CN105481901B - The metal complex of feux rouges containing iridium, preparation method and the organic electroluminescence device using the complex - Google Patents
The metal complex of feux rouges containing iridium, preparation method and the organic electroluminescence device using the complex Download PDFInfo
- Publication number
- CN105481901B CN105481901B CN201510874661.1A CN201510874661A CN105481901B CN 105481901 B CN105481901 B CN 105481901B CN 201510874661 A CN201510874661 A CN 201510874661A CN 105481901 B CN105481901 B CN 105481901B
- Authority
- CN
- China
- Prior art keywords
- compound
- parts
- added
- structural formula
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CCC(CC)OC1=CCC(*(c(cc2)ccc2OC)c(cc2)cc(C(*C)(*=C)c3c4)c2-c3cc(C(C)(CC)C*2c3)c4-c2ccc3NC)C=C1 Chemical compound CCC(CC)OC1=CCC(*(c(cc2)ccc2OC)c(cc2)cc(C(*C)(*=C)c3c4)c2-c3cc(C(C)(CC)C*2c3)c4-c2ccc3NC)C=C1 0.000 description 2
Classifications
-
- 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
Abstract
The present invention relates to a kind of metal complex of feux rouges containing iridium, preparation method and using the organic electroluminescence device of the complex.Wherein this contains iridium feux rouges metal complex, has the following structure：Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.For the metal complex of feux rouges containing iridium of the present invention compared with existing phosphor material, light, the thermal stability of material are high, can be with long-term preservation；Luminescence generated by light is high with electroluminescent efficiency；Synthesis technology is simple, of low cost, is the feux rouges phosphor material of function admirable.
Description
Technical field
The invention belongs to electroluminescent organic material technical fields, and in particular to a kind of metal complex of feux rouges containing iridium,
Preparation method and the organic electroluminescence device for using the complex.
Background technology
Organic electroluminescence device (Organic Light-Emitting Diodes, OLED) is due to, drive high with brightness
Dynamic voltage is low, it is light-weight, can be used for large area flexible display and prepare the advantages such as low with processing cost, by academia and industry
The extensive concern on boundary becomes the first choice of the following display technology.
According to the difference of principle of luminosity, electroluminescent organic material can be divided into fluorescence and phosphorescence two major classes.Due to phosphorescence
Material can utilize singlet and triplet excitons simultaneously, theoretically the internal quantum efficiency of device can be made to reach 100%.Cause
This, transient metal complex, which is widely used in, prepares efficient organic electroluminescence device.Wherein, complex of iridium is particularly
It is important, because it has suitable triplet lifetime and high luminous efficiency, and pass through the adjusting to the first and second ligands
It can realize shining for different wave length.
At the same time, phosphor material physical doping is also concerned to prepare organic luminescent device in the polymer.Cause
For on the one hand, which is utilized the machinable advantage of polymer solution, can pass through spin coating, silk-screen printing, inkjet printing etc.
Low cost process prepares device, avoids the shortcomings that small molecule material needs the high cost process such as vacuum evaporation；On the other hand,
The advantages of high-luminous-efficiency may be implemented in phosphor material is utilized again, so as to improve the luminous efficiency of device.
The phosphor material being used in white light OLED s has blue, green, red three primary colors.Wherein, satisfactory white to prepare
The red dye of light OLEDs, solution processable are essential.Currently, the red dye of efficient solution processing is very rare, limit
The development of feux rouges OLEDs and white light OLED s are made.
Therefore, develop can improve organic electroluminescence device luminescent properties feux rouges phosphorescent coloring be expand now it is red
One main trend of luminescent material research field.
Invention content
In order to solve the technical problems existing in the prior art, the purpose of the present invention is to provide a kind of metals of feux rouges containing iridium
Complex, preparation method and the organic electroluminescence device using the complex.
In order to solve the above-mentioned technical problem, technical scheme of the present invention is specific as follows：
A kind of metal complex of feux rouges containing iridium, has the following structure：
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
In the above-mentioned technical solutions,
The aryl be benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene or；
The heterocyclic aryl is pyrroles, pyridine, furans, thiophene or carbazole；
The substituent group of the substituted aryl or substituted heterocycle aryl is halogen atom, alkyl, alkoxy, amino, ester group, boric acid
Ester group, acyl group, amide groups, cyano, aryloxy group, aromatic radical or heterocyclic substituent；The substitution number of substituent group is one or more.
The preparation method of the above-mentioned metal complex of feux rouges containing iridium, includes the following steps：
(1) in protective gas atmosphere, 2- bromines fluorenes and tetrabutylammonium bromide are dissolved in dimethyl sulfoxide (DMSO), hydrogen-oxygen is added
The mass ratio for changing sodium and water is 1:Compound A is added in 1~3 sodium hydrate aqueous solution, reacts 6~24 hours, after isolating and purifying
Obtain compound B；Wherein, the structural formula of compound A is:The structural formula of R-Br, compound B isR
For alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl；
(2) in glacial acetic acid by compound B dissolvings, fuming nitric aicd is slowly added dropwise, cold bath is reacted 3~24 hours, separation
Compound C is obtained after purification, and the structural formula of compound C is
(3) at room temperature, compound C is dissolved in the in the mixed solvent of tetrahydrofuran and ethyl alcohol, tetrahydrofuran and ethyl alcohol
Volume ratio is 1:1~4, Pd/carbon catalyst is added, is heated to 60~70 DEG C, hydrazine hydrate is added dropwise, heating reaction 3~24 hours divides
From obtaining compound D after purification, the structural formula of compound D is
(4) it is 1 by molar ratio in protective gas atmosphere:2.1~3.0 compound D and 4- iodanisols are dissolved in pair
In dimethylbenzene, cuprous iodide/Phen is added as catalyst, potassium hydroxide is added, is heated to 100~145 DEG C of reactions 36
~48 hours, compound E is obtained after isolating and purifying, the structural formula of compound E is
(5) in protective gas atmosphere, compound E is dissolved in tetrahydrofuran (THF), at -78 DEG C, positive fourth is added
Base lithium reacts 40~60 minutes, and trimethyl borate is added, and reacts at room temperature 4~12 hours, and hydrochloric acid is added later makes the solution be in
It is acid；Compound F is obtained after isolating and purifying, the structural formula of compound F is
(6) it is 1 by molar ratio in protective gas atmosphere:1.1~2.0 2- chloro-5-trifluoromethylpyridines and chemical combination
Object F is dissolved in the first solvent, is added the aqueous solution of organic palladium catalyst and carbonate, carries out Suzuki coupling reactions 8~for 24 hours,
Compound G is obtained after isolating and purifying, the structural formula of compound is
(7) it is 2~3 by molar ratio in protective gas atmosphere:The 1 compound G and three hydrated iridium trichlorides are molten
It in the second solvent, is reacted 12~24 hours at 70~90 DEG C, compound H, the structural formula of the compound H is obtained after isolating and purifying
For
(8) it is 1 by molar ratio in protective gas atmosphere:3~5 compound H and acetylacetone,2,4-pentanedione is dissolved in third solvent
In, sodium carbonate is added, is heated to reacting 12~24 hours at 70~90 DEG C, the cooperation of feux rouges phosphorescent metal is obtained after isolating and purifying
The structural formula of object, the feux rouges phosphorescence iridium metal complex is
In the step (1), reactant dosage is with molfraction meter：2- bromine fluorenes is 1 part, and compound A is 2.1~3 parts,
Tetrabutylammonium bromide is 0.02~0.1 part, and sodium hydrate aqueous solution is 5~15 parts, and dimethyl sulfoxide (DMSO) is 2~5 parts；
In the step (2), reactant dosage is with molfraction meter：Compound B is 1 part, and fuming nitric aicd is 3~10
Part, glacial acetic acid is 2~50 parts；
In the step (3), reactant dosage is with molfraction meter：Compound C is 1 part, and hydrazine hydrate is 1.1~5 parts,
Pd/carbon catalyst is 0.05~0.15 part, and the mixed liquor of tetrahydrofuran and ethyl alcohol is 2~50 parts；
In the step (4), reactant dosage is with molfraction meter：Compound D be 1 part, 4- iodanisols be 2.1~
3 parts, cuprous iodide be 0.1~0.2 part, Phen be 0.2~0.4 part, potassium hydroxide be 7~10 parts, paraxylene be 2~
50 parts；
In the step (5), reactant dosage is with molfraction meter：Compound E be 1 part, n-BuLi be 1.1~
1.5 parts, trimethyl borate is 3~8 parts, and tetrahydrofuran is 2~50 parts.
In the above-mentioned technical solutions,
The first solvent in the step (6) is toluene or tetrahydrofuran；
The second solvent in the step (7) is the mixture of cellosolvo and water, the cellosolvo with
The volume ratio of water is 3:1；
Third solvent in the step (8) is cellosolvo.
In the above-mentioned technical solutions, organic palladium catalyst is tetra-triphenylphosphine palladium；Organic palladium catalyst and institute
The molar ratio for stating compound F and 2- chloro-5-trifluoromethylpyridines is 3:100-5:100.
In the above-mentioned technical solutions, the carbonate is at least one of potassium carbonate and sodium carbonate.
In the above-mentioned technical solutions, the specific of feux rouges phosphorescence iridium metal complex is obtained after being isolated and purified in step (8)
Method is：
After reaction, reaction solution is cooled to room temperature, removes at least partly third solvent, is extracted with dichloromethane, organic phase
It is washed with water three times, is dried with anhydrous magnesium sulfate, filter organic phase, the solvent removed in organic phase obtains solid crude product, with two
Chloromethanes and petroleum ether are eluant, eluent, and crude product purified by silica gel pillar layer separation is purified, and remove solvent and reuse two after dry
The mixed liquor of chloromethanes and methanol carries out being recrystallized to give the feux rouges phosphorescence iridium metal complex after purification.
Using the organic electroluminescence device of above-mentioned complex, including：
Substrate；
The anode being set on the substrate；
The number of the organic layer being set on the anode, organic layer is more than or equal to two, and one layer in organic layer is hair
Photosphere, electron injection/transport layer is on luminescent layer；
The cathode being set in electron injection/transport layer；
The material of the luminescent layer includes：Light emitting host material and the light-emitting guest material being doped in light emitting host material
Material；The light emitting guest material is the above-mentioned metal complex of feux rouges containing iridium.
In the above-mentioned technical solutions, the thickness of the electron injection/transport layer is 0.1~100nm；The thickness of the substrate
For 0.3~0.7mm.
In the above-mentioned technical solutions, the thickness of the electron injection/transport layer is 50nm.
The present invention has advantageous effect below：
The metal complex of feux rouges containing iridium of the present invention compared with existing phosphor material, with following technology imitate by the present invention
Fruit：
1, the light of material, thermal stability are high, can be with long-term preservation.
2, luminescence generated by light and electroluminescent efficiency are high.
3, synthesis technology is simple, of low cost, is the feux rouges phosphor material of function admirable.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the preparation method schematic diagram of the metal complex of feux rouges containing iridium of the present invention；
Fig. 2 is bis- [9,9- diethyl -7- (5- trifluoromethyl pyridines base) fluorenes] [N, N- (the 4- first of red phosphorescent of embodiment 1
Phenyl) amine-N, C] (acetylacetone,2,4-pentanedione) close complex of iridium electroluminescent spectrum；
Fig. 3 is current density-brightness-voltage characteristic figure of the organic electroluminescence device of embodiment 5；
Fig. 4 is the luminance-current efficiency figure of the organic electroluminescence device of embodiment 5.
Specific implementation mode
The present invention is described in detail below in conjunction with the accompanying drawings.
The present invention characterizes the structure of material by nuclear magnetic resonance, mass spectrum etc., passes through ultraviolet-visible and fluorescence emission spectrum
It has studied in detail photophysical property of these complexs under solution state, device simulation has been carried out by the method that solution is processed.
A kind of preparation method of the metal complex of feux rouges containing iridium, includes the following steps：
(1) in protective gas atmosphere, 2- bromines fluorenes and tetrabutylammonium bromide are dissolved in dimethyl sulfoxide (DMSO), addition is newly matched
Sodium hydrate aqueous solution (mass ratio of sodium hydroxide and water be 1:1~3) compound A, is added, reacts 6~24 hours, separation
Compound B is obtained after purification, and the structural formula of compound A is:The structural formula of R-Br, compound B isWherein
R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
In the step (1), reactant dosage is with molfraction meter：2- bromine fluorenes is 1 part, and compound A is 2.1~3 parts,
Tetrabutylammonium bromide is 0.02~0.1 part, and the sodium hydrate aqueous solution newly prepared is 5~15 parts, and dimethyl sulfoxide (DMSO) is 2~5 parts.
In the step of obtaining compound B after isolating and purifying, the method isolated and purified is specially：After reaction, acetic acid is used
Ethyl ester extracts, and organic phase three times, is dried with massive laundering with anhydrous magnesium sulfate, filters organic phase, removes the solvent in organic phase
Faint yellow solid crude product is obtained, is eluant, eluent with petroleum ether, crude product purified by silica gel pillar layer separation is purified, removes solvent,
Compound B after being purified after drying.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
(2) under ventilation condition, in glacial acetic acid by compound B dissolvings, fuming nitric aicd, cold bath reaction 3 is slowly added dropwise
~24 hours, compound C is obtained after isolating and purifying, the structural formula of compound C is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
In the step (2), reactant dosage is with molfraction meter：Compound B is 1 part, and fuming nitric aicd is 3~10
Part, glacial acetic acid is 2~50 parts.
In the step of obtaining compound C after isolating and purifying, the method isolated and purified is specially：After reaction, it is reacting
Sodium carbonate is added in liquid, makes reaction solution at alkalinity, is extracted with ethyl acetate, organic phase is washed with water three times, dry with anhydrous magnesium sulfate
It is dry, organic phase is filtered, the solvent removed in organic phase obtains faint yellow solid crude product, is elution with dichloromethane/petroleum ether
Agent purifies crude product purified by silica gel pillar layer separation, removes solvent, the compound C after being purified after dry.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
(3) at room temperature, compound C is dissolved in the in the mixed solvent of tetrahydrofuran and ethyl alcohol, tetrahydrofuran and ethyl alcohol
Volume ratio is 1:1~4, Pd/carbon catalyst is added, is heated to 60~70 DEG C, hydrazine hydrate is added dropwise, heating reaction 3~24 hours divides
From obtaining compound D after purification, the structural formula of compound D is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
In the step (3), reactant dosage is with molfraction meter：Compound C is 1 part, and hydrazine hydrate is 1.1~5 parts,
Pd/carbon catalyst is 0.05~0.15 part, and the mixed liquor of tetrahydrofuran and ethyl alcohol is 2~50 parts.
In the step of obtaining compound D after isolating and purifying, the method isolated and purified is specially：After reaction, acetic acid is used
Ethyl ester extracts, and organic phase three times, is dried with massive laundering with anhydrous magnesium sulfate, filters organic phase, removes the solvent in organic phase
Brown crude product is obtained, is eluant, eluent with dichloromethane/petroleum ether, crude product purified by silica gel pillar layer separation is purified, is removed molten
Agent, the compound D after being purified after dry.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
(4) it is 1 by molar ratio in protective gas atmosphere:2.1~3.0 compound D and 4- iodanisols are dissolved in pair
In dimethylbenzene, cuprous iodide/Phen is added as catalyst, potassium hydroxide is added, is heated to 100~145 DEG C of reactions 36
~48 hours, compound E is obtained after isolating and purifying, the structural formula of compound E is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
In the step (4), reactant dosage is with molfraction meter：Compound D be 1 part, 4- iodanisols be 2.1~
3 parts, cuprous iodide be 0.1~0.2 part, Phen be 0.2~0.4 part, potassium hydroxide be 7~10 parts, paraxylene be 2~
50 parts.
In the step of obtaining compound E after isolating and purifying, the method isolated and purified is specially：After reaction, it is cooled to room
Temperature is added a small amount of glacial acetic acid, is extracted with toluene, and organic phase is washed three times with aqueous sodium carbonate, is washed with water three times, with anhydrous sulphur
Sour magnesium drying, filters organic phase, the solvent removed in organic phase obtains solid crude product, is elution with dichloromethane/petroleum ether
Agent purifies crude product purified by silica gel pillar layer separation, removes solvent, the compound E after being purified after dry.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
(5) in protective gas atmosphere, compound E is dissolved in tetrahydrofuran (THF), at -78 DEG C, positive fourth is added
Base lithium reacts 40~60 minutes, and trimethyl borate is added, and reacts at room temperature 4~12 hours, and hydrochloric acid is added later makes the solution be in
It is acid.Compound F is obtained after isolating and purifying, the structural formula of compound F is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
In the step (5), reactant dosage is with molfraction meter：Compound E be 1 part, n-BuLi be 1.1~
1.5 parts, trimethyl borate is 3~8 parts, and tetrahydrofuran is 2~50 parts.
In the step of obtaining compound F after isolating and purifying, the method isolated and purified is specially：After reaction, ether is used
Extraction, organic phase are washed with water three times, are dried with anhydrous magnesium sulfate, filter organic phase, and the solvent removed in organic phase obtains solid
Crude product three times with petroleum ether removes solvent, the compound F after being purified after dry.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
(6) it is 1 by molar ratio in protective gas atmosphere:1.1~2.0 2- chloro-5-trifluoromethylpyridines and chemical combination
Object F is dissolved in the first solvent, is added the aqueous solution of organic palladium catalyst and carbonate, carries out Suzuki coupling reactions 8~for 24 hours,
Compound G is obtained after isolating and purifying, the structural formula of compound G is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
First solvent is toluene or tetrahydrofuran (THF).The dosage of first solvent is so that the chloro- 5- trifluoros of compound F and 2-
Picoline, which fully dissolves, to be advisable.
Organic palladium catalyst is tetra-triphenylphosphine palladium (Pd (PPh3)4), it is preferred that organic palladium catalyst and describedization
The molar ratio for closing object F and 2- chloro-5-trifluoromethylpyridines is 3:100-5:100.
The aqueous solution of carbonate is sodium carbonate or potassium carbonate.The molar ratio of carbonate is 2- chloro-5-trifluoromethylpyridines
3-5 times.
The method for isolating and purifying to obtain compound G is specially：After reaction, it is cooled to room temperature, is extracted with ethyl acetate, has
Machine is mutually washed with water three times, and organic phase is dried with anhydrous magnesium sulfate, filters organic phase, and the solvent removed in organic phase is consolidated
Body product, with silica gel column chromatography separating-purifying, removes solvent, is purified after dry using petroleum ether/dichloromethane as eluant, eluent
Compound G afterwards.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
(7) it is 2~3 by molar ratio in protective gas atmosphere:The 1 compound G and three hydrated iridium trichlorides are molten
It in the second solvent, is reacted 12~24 hours at 70~90 DEG C, compound H, the structural formula of the compound H is obtained after isolating and purifying
For
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
Second solvent is the mixture of cellosolvo and water, and the volume ratio of cellosolvo and water is 3:1.Second
The dosage of solvent is so that compound G and the dissolving of three hydrated iridium trichlorides are advisable.
After reaction, reaction solution is cooled to room temperature, and precipitating after water is added, collects solid after filtering, successively by the solid
It is washed using distilled water and methanol, the compound H after being purified after dry.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
(8) it is 1 by molar ratio in protective gas atmosphere:3~5 compound H and acetylacetone,2,4-pentanedione is dissolved in third solvent
In, sodium carbonate is added, is heated to reacting 12~24 hours at 70~90 DEG C, the cooperation of feux rouges phosphorescent metal is obtained after isolating and purifying
The structural formula of object, the feux rouges phosphorescence iridium metal complex is
Wherein R is alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl.
Protective gas is argon gas, nitrogen or neon.
Third solvent is cellosolvo.The dosage of third solvent is so that compound H and acetylacetone,2,4-pentanedione dissolving are advisable.
The mole of the sodium carbonate of addition is 5~10 times of compound H.
The method isolated and purified is：After reaction, reaction solution is cooled to room temperature, removes part third solvent, uses dichloromethane
Alkane extracts, and organic phase is washed with water three times, organic phase is dried with anhydrous magnesium sulfate, filters organic phase, removes in organic phase
Solvent obtains red solid, using petroleum ether/dichloromethane as eluant, eluent, with silica gel column chromatography separating-purifying, removes solvent, dry
The mixed liquor for reusing dichloromethane and methanol afterwards carries out being recrystallized to give the feux rouges phosphorescence iridium metal complex after purification.
It is appreciated that the method isolated and purified is not limited to the above method, above-mentioned reaction product can be isolated and purified
Method can be with.
The synthetic route of the above-mentioned metal complex of feux rouges containing iridium is as shown in Figure 1.
The preparation method reaction condition of the above-mentioned metal complex of feux rouges containing iridium is mild, manufacturing cost relatively low to equipment requirement
It is low, be conducive to mass produce.
Using the organic electroluminescence device of the metal complex of feux rouges containing iridium, including：
Substrate；
The anode being set on the substrate；
The number of the organic layer being set on the anode, organic layer is more than or equal to two, and one layer in organic layer is hair
Photosphere, electron injection/transport layer is on luminescent layer
The cathode being set in electron injection/transport layer.
The organic electro luminescent layer includes just compound described above.
The present invention does not have a particular/special requirement, preferably glass or plastics to the substrate, and the thickness of the substrate is 0.3~
0.7mm.According to the present invention, the anode is the material for being easy to hole transport, preferably conductive metal or conductive metal oxide,
More preferably indium tin oxide.
The organic layer can be multilayer, and at least one layer includes the chemical combination described in above-mentioned technical proposal in the luminescent layer
Object.The metal complex of feux rouges containing iridium can be used as dyestuff, and composition organic electro luminescent layer is doped with material of main part,
The present invention is not particularly limited the material of main part, is selected according to material well known to those skilled in the art.
After the organic layer is formed, electron injection/transport layer is formed on the surface thereof.The present invention to the electron injection/
The generation type of transport layer is not particularly limited, according to method well known to those skilled in the art.It can be added by solution
The mode spin-coating film of work.The material of the electron injection/transport layer is not particularly limited, according to known to those skilled in the art
Material.
The preferred metal of cathode, including but not limited to calcium, magnesium, barium, aluminium and silver, preferably aluminium.
In order to improve the performance and efficiency of device, the organic layer between the anode and organic electro luminescent layer preferably also wraps
Include hole injection layer, hole transmission layer and electronic barrier layer；Organic layer between the cathode and organic electro luminescent layer is preferred
Further include hole blocking layer.The present invention is to the hole injection layer, hole transmission layer, electronic barrier layer and hole blocking layer
Material and thickness there is no particular/special requirement, can be selected according to material well known to those skilled in the art and thickness.
The present invention is not particularly limited the preparation method of the organic electroluminescence device, can in accordance with the following methods into
Row：
Anode is formed over the substrate；
Multilayer organic layer is formed on the anode, wherein one layer is luminescent layer, it is hole blocking layer above luminescent layer.
Cathode is formed on the organic layer.
In preparing the organic electroluminescence device, anode is formed over the substrate first, the present invention is to formation side
Formula is not particularly limited, according to method well known to those skilled in the art.Invention does not have particular/special requirement to the substrate, excellent
Glass or plastics are selected as, the thickness of the substrate is 0.3~0.7mm.According to the present invention, the anode is to be easy to hole transport
Material, preferably conductive metal or conductive metal oxide, more preferably indium tin oxide.
After obtaining anode, organic layer is formed on the anode.Luminescent layer in the organic layer includes said program institute
The compound stated.The present invention is not particularly limited the generation type of the luminescent layer and luminescent layer organic layer below, can be with
It is formed on anode by solution spin coating, inkjet printing, hectographic printing or stereosopic printing.After the organic luminous layer is formed,
Hole blocking layer and electron injection/transport layer can be formed by way of vacuum evaporation or spin coating on the surface.The electronics
The preferred thickness of injection/transport layer is 0.1~100nm, more preferably 50~100nm.
After prepared by the organic layer, cathode is prepared on the surface thereof, and the anticathode preparation method of the present invention is not special
Limitation, method preferably well known to those skilled in the art including but not limited to deposit.The preferred metal of cathode, including but
It is not limited to calcium, magnesium, barium, aluminium and silver, preferably aluminium.
For a further understanding of the present invention, illustrated with reference to embodiment.Protection scope of the present invention is not by following
The limitation of embodiment.
It is specific embodiment below.
Bis- [9,9- diethyl -7- (5- trifluoromethyl pyridines base) fluorenes] [N, the N- (4- of 1 feux rouges phosphorescent iridium complex of embodiment
Methoxyphenyl) amine N, C] (acetylacetone,2,4-pentanedione) conjunction complex of iridium (metal complex of feux rouges containing iridium) and preparation method thereof.
Bis- [9,9- diethyl -7- (5- trifluoromethyl pyridines base) fluorenes] [N, N- (the 4- methoxybenzenes of feux rouges phosphorescent iridium complex
Base) amine N, C] (acetylacetone,2,4-pentanedione) close complex of iridium structural formula it is as follows：
(1) synthesis of the bromo- 9,9- diethyl fluorenes of 2-
Under protection of argon gas, 5.0g2- bromine fluorenes is dissolved in 10mL dimethyl sulfoxide (DMSO)s (DMSO), adds the 0.26g tetrabutyls
Ammonium bromide (TBABr), the sodium hydroxide solution that 10mL is newly prepared is added, and (mass ratio of sodium hydroxide and water is 1:1), after mixing,
4.8mL bromoethanes are added, are reacted 8 hours at 75 DEG C.After reaction, it is cooled to room temperature, is extracted with ethyl acetate, liquid separation is organic
Mutually three times with massive laundering, it is dried with anhydrous magnesium sulfate, filters organic phase, be that eluant, eluent carries out silica gel with petroleum ether after being spin-dried for
Pillar layer separation obtains solid 5.7g, yield 93% after dry.
(2) synthesis of the bromo- 9,9- diethyl fluorenes of 2- nitros -7-
Bromo- 9, the 9- diethyl fluorenes of the 2- of 3.5g is dissolved in the glacial acetic acid of 30mL, the smoke nitre of 2.8mL is slowly added dropwise
Acid reacts 4 hours under the conditions of cold bath.After having reacted, sodium carbonate, which is added, finally makes solution alkaline, is extracted later with ethyl acetate
It takes, liquid separation, organic phase is washed with water three times, is dried with anhydrous magnesium sulfate, organic phase is filtered, after being spin-dried for, with dichloromethane/petroleum ether
Silica gel column chromatography separation is carried out for eluant, eluent, light yellow solid 3.2g, yield 80% are obtained after dry.
(3) synthesis of the bromo- 9,9- diethyl fluorenes of 2- amino -7-
Bromo- 9, the 9- diethyl fluorenes of 3.5g2- nitros -7- is dissolved in the mixed liquor of tetrahydrofuran and ethyl alcohol, tetrahydrofuran
For 35mL, ethyl alcohol 20mL, 0.35g Pd/carbon catalysts are added, is heated to that the hydrazine hydrate of 16mL is slowly added dropwise at 70 DEG C, drips off
Afterwards, it reacts 12 hours.After reaction, it is cooled to room temperature, is extracted with ether, liquid separation, organic phase is washed with water three times, organic phase nothing
Water magnesium sulfate is dried, and organic phase is filtered, and after being spin-dried for, dichloromethane/petroleum ether is used to carry out silica gel chromatograph separation as eluant, eluent, done
Rufous oily liquids 2.2g, yield 69% are obtained after dry.
(4) synthesis of bromo- 9,9- diethyl fluorenes-N, the N-4- methoxy diphenylamines of 7-
Under protection of argon gas, by bromo- 9, the 9- diethyl fluorenes of 1.8g2- amino -7-, 3.3g4- iodanisols, 0.11g iodate
Cuprous, 0.22g Phens and 2.2g potassium hydroxide is melt and dissolved is vigorously stirred in 30mL paraxylene, 100 DEG C of reactions 36 are small
When.After reaction, it is cooled to room temperature, 25mL glacial acetic acid is added, is extracted with toluene, liquid separation, organic phase is washed with aqueous sodium carbonate
Three times, it is washed with water three times, organic phase is dried with anhydrous magnesium sulfate, organic phase is filtered, after being spin-dried for, with dichloromethane/petroleum ether
Silica gel chromatograph separation is carried out as eluant, eluent, solid 1.6g, yield 53% are obtained after dry.
(5) synthesis of N, N-4- methoxy diphenylamine base -9,9- diethyl fluorenes boric acid
Under protection of argon gas, bromo- 9,9- diethyl fluorenes-N, the N-4- methoxy diphenylamines of 2.0g7- are dissolved in 30mL dryings
Tetrahydrofuran in, at -78 DEG C, be added the n-BuLi of 2.4mL, react 1 hour, the trimethyl boric acid of 2.1mL is added later
Ester reacts 4 hours at room temperature.After reaction, the hydrochloric acid of 2mol/L, which is added, makes solution in acidity, is extracted with ether, liquid separation has
Machine is mutually washed with water three times, and organic phase is dried with anhydrous magnesium sulfate, filters organic phase, after being spin-dried for, three times with petroleum ether, is not necessarily to
Further purification can be directly used as reacting in next step.White solid 1.8g, yield 97% are obtained after drying.
(6) synthesis of [9,9- diethyl -7- (5- trifluoromethyl pyridines base) fluorenes] [N, N- (4- methoxyphenyls)] amine
Under protection of argon gas, by 0.49g2- chloro-5-trifluoromethylpyridines, 2.gN, N-4- methoxy diphenylamine bases -9,9-
The solution of potassium carbonate of diethyl fluorenes boric acid, 0.1g tetra-triphenylphosphine palladiums and 9mL2mol/L is added in 50mL toluene, at 110 DEG C
It is stirred to react 24 hours.It after having reacted, is extracted with ethyl acetate, liquid separation, is washed to neutrality, anhydrous magnesium sulfate drying.Filtering, rotation
After dry, it is that eluant, eluent carries out silica gel column chromatography separation with petroleum ether/dichloromethane, greenish yellow solid 1.0g, yield is obtained after dry
63%.
(7) [9,9- diethyl -7- (5- trifluoromethyl pyridines base) fluorenes] [N, N- (4- methoxyphenyls)] amine that ligand is
The synthesis of the dimer of dichloro containing iridium
Under protection of argon gas, tri- chloride hydrate iridium of 0.1g, 0.5g ligands [9,9- diethyl -7- (5- trifluoromethyl pyridines
Base) fluorenes] [N, N- (4- methoxyphenyls)] amine is dissolved in mixed liquor (cellosolvo and the water of 6mL2- ethoxy ethanols and water
Volume ratio be 3:1) it in, is stirred to react at 80 DEG C 24 hours.After being cooled to room temperature, rotation boils off partial solvent, and appropriate steam is added
Distilled water, filtering.Solid is washed with distilled water, methanol successively, it is dry after solid 0.48g, yield 72%,.Dimer is not necessarily to
Further purification can direct plunge into reacting in next step.
(8) bis- [9,9- diethyl -7- (5- trifluoromethyl pyridines base) fluorenes] [N, N- (4- methoxyphenyls) amine N, C] (second
Acyl acetone) close complex of iridium synthesis
Under protection of argon gas, 0.48g ligands are [9,9- diethyl -7- (5- trifluoromethyl pyridines base) fluorenes] [N, N- (4- first
Phenyl)] dimer of dichloro containing iridium of amine and 0.1g acetylacetone,2,4-pentanediones be dissolved in 6mL2- ethoxy ethanols, 0.2g carbonic acid is added
Sodium is stirred to react 18 hours at 80 DEG C.After being cooled to room temperature, partial solvent is removed, appropriate distilled water is added, is extracted with dichloromethane
It takes, liquid separation, is washed to neutrality, anhydrous magnesium sulfate drying, the solvent removed in organic phase obtains red solid, with petroleum ether/bis-
Chloromethanes (volume ratio 1:1) it is eluant, eluent, with silica gel column chromatography separating-purifying, removes solvent and use dichloromethane after dry
It carries out being recrystallized to give red solid 0.15g with the mixed liquor of methanol, is 60% by yield.Through nuclear magnetic resonance spectroscopy,1H
NMR (400MHz, DMSO) δ 8.59 (s, 2H), 8.41 (d, J=8.8Hz, 2H), 8.26 (d, J=8.9Hz, 2H), 7.81 (s,
2H), 6.97 (d, J=8.3Hz, 2H), 6.87 (d, J=9.0Hz, 8H), 6.80 (d, J=9.0Hz, 8H), 6.68 (d, J=
1.7Hz, 2H), 6.57 (dd, J=8.3,1.8Hz, 2H), 6.22 (s, 2H), 5.32 (s, 1H), 3.66 (s, 12H), 1.86 (dd,
J=13.5,7.2Hz, 3H), 1.78-1.65 (m, 8H), 1.65-1.48 (m, 3H), 0.26 (t, J=7.3Hz, 6H) ,-0.00
(t, J=7.2Hz, 6H)13C NMR(101MHz,CDCl3)δ185.14,172.42,155.37,152.44,148.50,
145.26,143.91,142.55,141.26,140.18,134.05,133.43,125.76,122.79,120.46,120.31,
119.60,117.72,116.02,114.44,100.67,77.26,76.92,76.60,55.33,55.04,32.85,32.23,
29.59,28.53,8.80,8.50. mass spectrum (MS m/z)：1478.5. electroluminescent spectrum is as shown in Figure 1.
Another metal complex of feux rouges containing iridium of embodiment 2 and preparation method thereof.
Present embodiment and embodiment 1 difference lies in：
The structure of the metal complex of feux rouges containing iridium is
Wherein, R is naphthalene.
In the preparation process of the metal complex of feux rouges containing iridium, difference from example 1 is that following steps：
(1) in sodium hydrate aqueous solution, the mass ratio of sodium hydroxide and water is 1:3；After compound A is added, reaction 6 is small
When；
(2) in glacial acetic acid by compound B dissolvings, fuming nitric aicd is slowly added dropwise, cold bath is reacted 3 hours；
(3) volume ratio of tetrahydrofuran and ethyl alcohol is 1:4；Pd/carbon catalyst is added, is heated to 65 DEG C, hydrazine hydrate is added dropwise,
Heating reaction 3 hours, obtains compound D after isolating and purifying；
(4) it is 1 by molar ratio in protective gas atmosphere:3.0 compound D is dissolved in 4- iodanisols to diformazan
In benzene, cuprous iodide/Phen is added as catalyst, potassium hydroxide is added, is heated to 120 DEG C and reacts 42 hours, separation
Compound E is obtained after purification；
(5) in protective gas atmosphere, compound E is dissolved in tetrahydrofuran THF, at -78 DEG C, normal-butyl is added
Lithium reacts 40 minutes, and trimethyl borate is added, and reacts at room temperature 8 hours, and hydrochloric acid is added later makes solution in acidity；
(6) it is 1 by molar ratio in protective gas atmosphere:1.1 2- chloro-5-trifluoromethylpyridines and compound F is molten
In the first solvent, the aqueous solution of organic palladium catalyst and carbonate is added, Suzuki coupling reaction 8h are carried out, after isolating and purifying
Obtain compound G；
(7) it is 2 by molar ratio in protective gas atmosphere:The 1 compound G and three hydrated iridium trichlorides are dissolved in
In second solvent, reacted 16 hours at 70 DEG C；
(8) it is 1 by molar ratio in protective gas atmosphere:3 compound H and acetylacetone,2,4-pentanedione is dissolved in third solvent,
Sodium carbonate is added, is heated to reacting 12 hours at 70 DEG C.
In the step (1), reactant dosage is with molfraction meter：2- bromine fluorenes be 1 part, compound A be 2.1 parts, four
Butylammonium bromide is 0.02 part, and sodium hydrate aqueous solution is 5 parts, and dimethyl sulfoxide (DMSO) is 2 parts；
In the step (2), reactant dosage is with molfraction meter：Compound B is 1 part, and fuming nitric aicd is 3 parts, ice
Acetic acid is 2 parts；
In the step (3), reactant dosage is with molfraction meter：Compound C is 1 part, and hydrazine hydrate is 1.1 parts, palladium/
Pd/carbon catalyst is 0.05 part, and the mixed liquor of tetrahydrofuran and ethyl alcohol is 2 parts；
In the step (4), reactant dosage is with molfraction meter：Compound D is 1 part, and 4- iodanisols are 2.1
Part, cuprous iodide is 0.1 part, and Phen is 0.2 part, and potassium hydroxide is 7 parts, and paraxylene is 2 parts；
In the step (5), reactant dosage is with molfraction meter：Compound E is 1 part, and n-BuLi is 1.1 parts,
Trimethyl borate is 3 parts, and tetrahydrofuran is 2 parts.
The first solvent in the step (6) is tetrahydrofuran.
Embodiment 3 and another metal complex of feux rouges containing iridium and preparation method thereof.
Present embodiment and embodiment 1 difference lies in：
The structure of the metal complex of feux rouges containing iridium is
Wherein, R is pyrroles.
In the preparation process of the metal complex of feux rouges containing iridium, difference from example 1 is that following steps：
(1) in sodium hydrate aqueous solution, the mass ratio of sodium hydroxide and water is 1:2；After compound A is added, reaction 24 is small
When；
(2) in glacial acetic acid by compound B dissolvings, fuming nitric aicd is slowly added dropwise, cold bath is reacted 24 hours；
(3) volume ratio of tetrahydrofuran and ethyl alcohol is 1:3；Pd/carbon catalyst is added, is heated to 70 DEG C, hydrazine hydrate is added dropwise,
Heating reaction 24 hours, obtains compound D after isolating and purifying；
(4) it is 1 by molar ratio in protective gas atmosphere:2.1 compound D is dissolved in 4- iodanisols to diformazan
In benzene, cuprous iodide/Phen is added as catalyst, potassium hydroxide is added, is heated to 145 DEG C and reacts 36 hours, separation
Compound E is obtained after purification；
(5) in protective gas atmosphere, compound E is dissolved in tetrahydrofuran THF, at -78 DEG C, normal-butyl is added
Lithium reacts 50 minutes, and trimethyl borate is added, and reacts at room temperature 12 hours, and hydrochloric acid is added later makes solution in acidity；
(6) it is 1 by molar ratio in protective gas atmosphere:2.0 2- chloro-5-trifluoromethylpyridines and compound F is molten
In the first solvent, the aqueous solution of organic palladium catalyst and carbonate is added, carries out Suzuki coupling reaction 16h, isolates and purifies
After obtain compound G；
(7) it is 3 by molar ratio in protective gas atmosphere:The 1 compound G and three hydrated iridium trichlorides are dissolved in
In second solvent, reacted 12 hours at 90 DEG C；
(8) it is 1 by molar ratio in protective gas atmosphere:5 compound H and acetylacetone,2,4-pentanedione is dissolved in third solvent,
Sodium carbonate is added, is heated to reacting 24 hours at 90 DEG C.
In the step (1), reactant dosage is with molfraction meter：2- bromine fluorenes is 1 part, and compound A is 3 parts, four fourths
Base ammonium bromide is 0.1 part, and sodium hydrate aqueous solution is 15 parts, and dimethyl sulfoxide (DMSO) is 5 parts；
In the step (2), reactant dosage is with molfraction meter：Compound B is 1 part, and fuming nitric aicd is 10 parts, ice
Acetic acid is 50 parts；
In the step (3), reactant dosage is with molfraction meter：Compound C is 1 part, and hydrazine hydrate is 5 parts, palladium/charcoal
Catalyst is 0.15 part, and the mixed liquor of tetrahydrofuran and ethyl alcohol is 50 parts；
In the step (4), reactant dosage is with molfraction meter：Compound D is 1 part, and 4- iodanisols are 3 parts,
Cuprous iodide is 0.2 part, and Phen is 0.4 part, and potassium hydroxide is 10 parts, and paraxylene is 50 parts；
In the step (5), reactant dosage is with molfraction meter：Compound E is 1 part, and n-BuLi is 1.5 parts,
Trimethyl borate is 8 parts, and tetrahydrofuran is 50 parts.
In other specific implementation modes, R can also be alkyl, aryl, substituted aryl, heterocyclic aryl or substituted heterocycle
Aryl；The preferred aryl be benzene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene or；The heterocyclic aryl is pyrroles, pyridine, furans, thiophene
Pheno or carbazole；The substituent group of the substituted aryl or substituted heterocycle aryl is halogen atom, alkyl, alkoxy, amino, ester group, boron
Perester radical, acyl group, amide groups, cyano, aryloxy group, aromatic radical or heterocyclic substituent；The substitution number of substituent group is one or more
It is a.
The organic electroluminescence device of 4 metal complex of feux rouges containing iridium using the present invention of embodiment.
The organic electroluminescence device of the metal complex of feux rouges containing iridium using the present invention, including：Substrate is set to described
Anode on substrate, the organic layer being set on the anode, the cathode being set in electron injection/transport layer.
Wherein, the number of organic layer is two layers, and it is luminescent layer to have one layer of organic layer, and electron injection/transport layer is in luminescent layer
On；The material of the anode is indium tin oxide.The material of the luminescent layer includes light emitting host material and is doped in luminous
Light emitting guest material in material of main part, the light emitting guest material are the metal complex of feux rouges containing iridium in above-described embodiment.
The thickness of the electron injection/transport layer is 0.1nm.The thickness of the substrate is 0.3mm.
The preferred metal of cathode, including but not limited to calcium, magnesium, barium, aluminium and silver, preferably aluminium.
In other specific implementation modes, the number of organic layer can also be for 3 layers or more, wherein one layer of organic layer is
Luminescent layer；The thickness of the electron injection/transport layer may be 50nm or 100nm.The thickness of the substrate may be
0.5mm or 0.7mm.
The preparation of the organic electroluminescence device of 5 metal complex of feux rouges containing iridium using the present invention of embodiment.
Indium tin oxide-coated glass (ito glass) first is cleaned with tin indium oxide (ITO) cleaning agent, then wash with distilled water,
Last UV ozone (UVO) handles 25min；With 3000 revs/min of speed on indium tin oxide-coated glass the poly- ethylene of spin coating two
Oxygen thiophene-poly- (styrene sulfonate) (PEDOT) one minute, 120 DEG C are dried 1 hour, and the anode of organic electroluminescence device is obtained.
The anode is set on substrate.
By 10mg4,4', 4 "-three (N-3- methylphenyl-N-phenyls amino) triphenylamines (m-MTDATA) are made with embodiment 1
Standby complex of iridium and the mixing of 1mL chlorobenzenes, are configured to the chlorobenzene solution of 10mg/mL, then with 1500 revs/min of speed in the sun
Extremely upper spin coating one minute, 100 DEG C of heat treatment 30min, obtain organic electro luminescent layer in an inert atmosphere；
By the organic electro luminescent layer 4 × 10-4Under the vacuum degree of Pa, electron injection/transport layer of 50nm thickness is deposited
The Al, the LiF of LiF and the 100nm thickness of 1nm thickness is deposited in 1,3,5- tri- [(3- pyridyl groups) -3- phenyl] benzene (TmPyPB) later
It is compound negative electrode with Al, it is ITO/PEDOT to finally obtain structure:PSS(40nm)/m-MTDATA：X wt.% complex of iridium/
TmPyPB (60nm)/LiF (1nm)/Al (100nm) organic electroluminescence device.
As shown in Figures 3 and 4, had by the sources Keithley measuring system (Keithley2400Sourcemeter) test is above-mentioned
Organic electroluminescence devices current-voltage-brightness characteristic tests its electricity with SpectraScan PR650spectrophotometer
Photoluminescence spectrum.All measurements carry out under atmosphere at room temperature.It is 2.4V to measure organic electroluminescence device and open bright voltage, maximum
Luminous efficiency is 24.5%, maximum power efficiency 31.2lm/W.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (9)
1. a kind of metal complex of feux rouges containing iridium, which is characterized in that have the following structure：
Wherein R is ethyl, naphthalene or pyrrole radicals；
The metal complex of feux rouges containing iridium is prepared by following methods：
(1) in protective gas atmosphere, 2- bromines fluorenes and tetrabutylammonium bromide are dissolved in dimethyl sulfoxide (DMSO), sodium hydroxide is added
Mass ratio with water is 1:Compound A is added in 1~3 sodium hydrate aqueous solution, reacts 6~24 hours, is obtained after isolating and purifying
Compound B；Wherein, the structural formula of compound A is:The structural formula of R-Br, compound B isR is second
Base, naphthalene or pyrrole radicals；
(2) in glacial acetic acid by compound B dissolvings, fuming nitric aicd is slowly added dropwise, cold bath is reacted 3~24 hours, isolated and purified
After obtain compound C, the structural formula of compound C is
(3) at room temperature, compound C is dissolved in the in the mixed solvent of tetrahydrofuran and ethyl alcohol, the volume of tetrahydrofuran and ethyl alcohol
Than being 1:1~4, Pd/carbon catalyst is added, is heated to 60~70 DEG C, hydrazine hydrate is added dropwise, heating reaction 3~24 hours, separation is pure
Compound D is obtained after change, the structural formula of compound D is
(4) it is 1 by molar ratio in protective gas atmosphere:2.1~3.0 compound D is dissolved in 4- iodanisols to diformazan
In benzene, cuprous iodide/Phen is added as catalyst, potassium hydroxide is added, is heated to 100~145 DEG C of reactions 36~48
Hour, compound E is obtained after isolating and purifying, the structural formula of compound E is
(5) in protective gas atmosphere, compound E is dissolved in tetrahydrofuran, at -78 DEG C, n-BuLi, reaction is added
40~60 minutes, trimethyl borate is added, reacts at room temperature 4~12 hours, hydrochloric acid is added later makes solution in acidity；Separation
Compound F is obtained after purification, and the structural formula of compound F is
(6) it is 1 by molar ratio in protective gas atmosphere:1.1~2.0 2- chloro-5-trifluoromethylpyridines and compound F
It is dissolved in the first solvent, is added the aqueous solution of organic palladium catalyst and carbonate, carry out Suzuki coupling reactions 8~for 24 hours, separation
Compound G is obtained after purification, and the structural formula of compound is
(7) it is 2~3 by molar ratio in protective gas atmosphere:The 1 compound G and three hydrated iridium trichlorides are dissolved in
It in two solvents, is reacted 12~24 hours at 70~90 DEG C, compound H is obtained after isolating and purifying, the structural formula of the compound H is
(8) it is 1 by molar ratio in protective gas atmosphere:3~5 compound H and acetylacetone,2,4-pentanedione is dissolved in third solvent,
Sodium carbonate is added, is heated to reacting 12~24 hours at 70~90 DEG C, the metal complex of feux rouges containing iridium, institute is obtained after isolating and purifying
The structural formula for stating the metal complex of feux rouges containing iridium is
In the step (1), reactant dosage is with molfraction meter：2- bromine fluorenes is 1 part, and compound A is 2.1~3 parts, four fourths
Base ammonium bromide is 0.02~0.1 part, and sodium hydrate aqueous solution is 5~15 parts, and dimethyl sulfoxide (DMSO) is 2~5 parts；
In the step (2), reactant dosage is with molfraction meter：Compound B is 1 part, and fuming nitric aicd is 3~10 parts, ice
Acetic acid is 2~50 parts；
In the step (3), reactant dosage is with molfraction meter：Compound C is 1 part, and hydrazine hydrate is 1.1~5 parts, palladium/
Pd/carbon catalyst is 0.05~0.15 part, and the mixed liquor of tetrahydrofuran and ethyl alcohol is 2~50 parts；
In the step (4), reactant dosage is with molfraction meter：Compound D is 1 part, and 4- iodanisols are 2.1~3 parts,
Cuprous iodide is 0.1~0.2 part, and Phen is 0.2~0.4 part, and potassium hydroxide is 7~10 parts, and paraxylene is 2~50
Part；
In the step (5), reactant dosage is with molfraction meter：Compound E is 1 part, and n-BuLi is 1.1~1.5 parts,
Trimethyl borate is 3~8 parts, and tetrahydrofuran is 2~50 parts.
2. the preparation method of the metal complex of feux rouges containing iridium described in claim 1, which is characterized in that include the following steps：
(1) in protective gas atmosphere, 2- bromines fluorenes and tetrabutylammonium bromide are dissolved in dimethyl sulfoxide (DMSO), sodium hydroxide is added
Mass ratio with water is 1:Compound A is added in 1~3 sodium hydrate aqueous solution, reacts 6~24 hours, is obtained after isolating and purifying
Compound B；Wherein, the structural formula of compound A is:The structural formula of R-Br, compound B isR is second
Base, naphthalene or pyrrole radicals；
(2) in glacial acetic acid by compound B dissolvings, fuming nitric aicd is slowly added dropwise, cold bath is reacted 3~24 hours, isolated and purified
After obtain compound C, the structural formula of compound C is
(3) at room temperature, compound C is dissolved in the in the mixed solvent of tetrahydrofuran and ethyl alcohol, the volume of tetrahydrofuran and ethyl alcohol
Than being 1:1~4, Pd/carbon catalyst is added, is heated to 60~70 DEG C, hydrazine hydrate is added dropwise, heating reaction 3~24 hours, separation is pure
Compound D is obtained after change, the structural formula of compound D is
(4) it is 1 by molar ratio in protective gas atmosphere:2.1~3.0 compound D is dissolved in 4- iodanisols to diformazan
In benzene, cuprous iodide/Phen is added as catalyst, potassium hydroxide is added, is heated to 100~145 DEG C of reactions 36~48
Hour, compound E is obtained after isolating and purifying, the structural formula of compound E is
(5) in protective gas atmosphere, compound E is dissolved in tetrahydrofuran, at -78 DEG C, n-BuLi, reaction is added
40~60 minutes, trimethyl borate is added, reacts at room temperature 4~12 hours, hydrochloric acid is added later makes solution in acidity；Separation
Compound F is obtained after purification, and the structural formula of compound F is
(6) it is 1 by molar ratio in protective gas atmosphere:1.1~2.0 2- chloro-5-trifluoromethylpyridines and compound F
It is dissolved in the first solvent, is added the aqueous solution of organic palladium catalyst and carbonate, carry out Suzuki coupling reactions 8~for 24 hours, separation
Compound G is obtained after purification, and the structural formula of compound is
(7) it is 2~3 by molar ratio in protective gas atmosphere:The 1 compound G and three hydrated iridium trichlorides are dissolved in
It in two solvents, is reacted 12~24 hours at 70~90 DEG C, compound H is obtained after isolating and purifying, the structural formula of the compound H is
(8) it is 1 by molar ratio in protective gas atmosphere:3~5 compound H and acetylacetone,2,4-pentanedione is dissolved in third solvent,
Sodium carbonate is added, is heated to reacting 12~24 hours at 70~90 DEG C, the metal complex of feux rouges containing iridium, institute is obtained after isolating and purifying
The structural formula for stating the metal complex of feux rouges containing iridium is
In the step (1), reactant dosage is with molfraction meter：2- bromine fluorenes is 1 part, and compound A is 2.1~3 parts, four fourths
Base ammonium bromide is 0.02~0.1 part, and sodium hydrate aqueous solution is 5~15 parts, and dimethyl sulfoxide (DMSO) is 2~5 parts；
In the step (2), reactant dosage is with molfraction meter：Compound B is 1 part, and fuming nitric aicd is 3~10 parts, ice
Acetic acid is 2~50 parts；
In the step (3), reactant dosage is with molfraction meter：Compound C is 1 part, and hydrazine hydrate is 1.1~5 parts, palladium/
Pd/carbon catalyst is 0.05~0.15 part, and the mixed liquor of tetrahydrofuran and ethyl alcohol is 2~50 parts；
In the step (4), reactant dosage is with molfraction meter：Compound D is 1 part, and 4- iodanisols are 2.1~3 parts,
Cuprous iodide is 0.1~0.2 part, and Phen is 0.2~0.4 part, and potassium hydroxide is 7~10 parts, and paraxylene is 2~50
Part；
In the step (5), reactant dosage is with molfraction meter：Compound E is 1 part, and n-BuLi is 1.1~1.5 parts,
Trimethyl borate is 3~8 parts, and tetrahydrofuran is 2~50 parts.
3. preparation method according to claim 2, which is characterized in that
The first solvent in the step (6) is toluene or tetrahydrofuran；
The second solvent in the step (7) is the mixture of cellosolvo and water, the cellosolvo and water
Volume ratio is 3:1；
Third solvent in the step (8) is cellosolvo.
4. preparation method according to claim 2, which is characterized in that organic palladium catalyst is tetra-triphenylphosphine palladium；
The molar ratio of organic palladium catalyst and the compound F and 2- chloro-5-trifluoromethylpyridines is 3:100-5:100.
5. preparation method according to claim 2, which is characterized in that the carbonate be in potassium carbonate and sodium carbonate extremely
Few one kind.
6. preparation method according to claim 2, which is characterized in that obtained after being isolated and purified in step (8) red containing iridium
The specific method of light metal complex is：
After reaction, reaction solution is cooled to room temperature, removes at least partly third solvent, is extracted with dichloromethane, organic phase water
It washes three times, is dried with anhydrous magnesium sulfate, filter organic phase, the solvent removed in organic phase obtains solid crude product, uses dichloromethane
Alkane and petroleum ether are eluant, eluent, and crude product purified by silica gel pillar layer separation is purified, and remove solvent and reuse dichloromethane after dry
The mixed liquor of alkane and methanol carries out being recrystallized to give the metal complex of feux rouges containing iridium after purification.
7. using the organic electroluminescence device of complex described in claim 1, which is characterized in that including what is stacked gradually：
Anode, luminescent layer and cathode；
The material of the luminescent layer includes：Light emitting host material and the light emitting guest material being doped in light emitting host material；
The light emitting guest material is the metal complex of feux rouges containing iridium described in claim 1.
8. organic electroluminescence device according to claim 7, which is characterized in that the thickness of the electron injection/transport layer
Degree is 0.1~100nm；The thickness of the substrate is 0.3~0.7mm.
9. organic electroluminescence device according to claim 8, which is characterized in that the thickness of the electron injection/transport layer
Degree is 50nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510874661.1A CN105481901B (en) | 2015-12-03 | 2015-12-03 | The metal complex of feux rouges containing iridium, preparation method and the organic electroluminescence device using the complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510874661.1A CN105481901B (en) | 2015-12-03 | 2015-12-03 | The metal complex of feux rouges containing iridium, preparation method and the organic electroluminescence device using the complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105481901A CN105481901A (en) | 2016-04-13 |
| CN105481901B true CN105481901B (en) | 2018-09-14 |
Family
ID=55669215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510874661.1A Active CN105481901B (en) | 2015-12-03 | 2015-12-03 | The metal complex of feux rouges containing iridium, preparation method and the organic electroluminescence device using the complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105481901B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6848342B2 (en) * | 2016-10-26 | 2021-03-24 | 株式会社リコー | Electrochromic compositions and electrochromic devices |
| CN107236006B (en) * | 2017-07-10 | 2020-08-25 | 中国科学院长春应用化学研究所 | Red light metal complex and organic electroluminescent device thereof |
| CN107722061B (en) * | 2017-09-30 | 2020-05-05 | 南京邮电大学 | Fluorenyl oxadiazole iridium complex and preparation method and application thereof |
| CN107722060A (en) * | 2017-09-30 | 2018-02-23 | 南京邮电大学 | A kind of fluorenyl tetrazole complex of iridium and its preparation method and application |
| CN109988099B (en) * | 2019-04-24 | 2021-02-23 | 武汉华星光电半导体显示技术有限公司 | Electroluminescent material, preparation method of electroluminescent material and luminescent device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101170853A (en) * | 2007-11-23 | 2008-04-30 | 电子科技大学 | A white light organic EL part consisting of RGB and its making method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7652136B2 (en) * | 2005-11-15 | 2010-01-26 | The Hong Kong University Of Science And Technology | Diarylaminofluorene-based organometallic phosphors and organic light-emitting devices made with such compounds |
-
2015
- 2015-12-03 CN CN201510874661.1A patent/CN105481901B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101170853A (en) * | 2007-11-23 | 2008-04-30 | 电子科技大学 | A white light organic EL part consisting of RGB and its making method |
Non-Patent Citations (2)
| Title |
|---|
| Ambipolar organic light-emitting electrochemical transistor based on a heteroleptic charged iridium(III) complex;Ye Zhou等;《Appl. Phys. Lett.》;20130225;第102卷(第8期);第083301-1-083301-4页 * |
| Efficient Polymer White-Light-Emitting Devices for Solid-State Lighting;Hongbin Wu等;《Adv. Mater.》;Wiley;20090610;第21卷;第4181-4184页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105481901A (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101490207B (en) | Novel materials for organic electroluminescent devices | |
| JP5406305B2 (en) | Electroluminescent device using electroluminescent compound as luminescent material | |
| CN105481901B (en) | The metal complex of feux rouges containing iridium, preparation method and the organic electroluminescence device using the complex | |
| JP2009249385A (en) | New organic electroluminescent compound, and organic electroluminescent element using the same | |
| CN104513247B (en) | A kind of benzo ［ c ］ benzo ［ 3,4 ］ carbazole and carbazole derivates and application | |
| CN108276428A (en) | Perimidine derivative and application | |
| CN106684252A (en) | Organic light emitting device (OLED) of double-main-body structure | |
| CN104649955B (en) | A kind of naphthocarbazole derivative and its application in organic electroluminescence device | |
| CN104673276B (en) | A kind of luminous organic material and its application | |
| He et al. | Light-emitting dyes derived from bifunctional chromophores of diarylamine and oxadiazole: Synthesis, crystal structure, photophysics and electroluminescence | |
| CN108203407A (en) | Pyrene class electroluminescent organic material, luminescent device and display | |
| CN107312017A (en) | A kind of electroluminescent organic material and its organic luminescent device of Han phenoxazines/Sai oxazine analog derivatives | |
| CN101547878B (en) | Benzo [a] fluoranthene compound and organic light emitting device using the same | |
| CN106632514B (en) | A kind of phosphorescence PtAg2Complex and its preparation method and application | |
| CN107445996A (en) | Pyridazine class iridium complex phosphorescence material of butterfly alkene modification and its preparation method and application | |
| CN109503427B (en) | D-A type organic blue fluorescent material and preparation method and application thereof | |
| CN107602574A (en) | A kind of compound and its application using cyano group benzene as core | |
| CN107759559A (en) | Compound and its organic electronic device | |
| CN107619406A (en) | A kind of new carbazole analog derivative and preparation method thereof and application in the devices | |
| CN111825671A (en) | Compound containing carbazole ring and application thereof | |
| KR20100130059A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| CN107236006B (en) | Red light metal complex and organic electroluminescent device thereof | |
| CN104513192B (en) | A kind of benzo anthra [9,1-bc] carbazole derivates and its application | |
| CN109206367A (en) | A kind of organic electroluminescence device and display | |
| CN109206368A (en) | A kind of dihydrobenzo indazole class electroluminescent organic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xie Zhiyuan Inventor after: Liu Xuejing Inventor after: Zhang Baohua Inventor after: Wu Jiang Inventor before: Xie Zhiyuan Inventor before: Wu Jiang Inventor before: Zhang Xiaoqin |
|
| COR | Change of bibliographic data | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Baohua Inventor after: Liu Xuejing Inventor after: Xie Zhiyuan Inventor after: Wu Jiang Inventor before: Xie Zhiyuan Inventor before: Liu Xuejing Inventor before: Zhang Baohua Inventor before: Wu Jiang |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |