CN107573386A - Complex of iridium containing thieno [2,3 d] pyrimidine group and the application in electroluminescent device - Google Patents
Complex of iridium containing thieno [2,3 d] pyrimidine group and the application in electroluminescent device Download PDFInfo
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Abstract
The invention discloses the complex of iridium containing thieno [2,3 d] pyrimidine group and its application as phosphorescent guest material in organic electroluminescence device.Main part in the serial complex of iridium molecule is the derivative containing thieno [2,3 d] pyrimidine heterocyclic.Assistant ligand is acetylacetone,2,4-pentanedione, dipivaloylmethane or 2 pyridine carboxylic acids.This kind of complex of iridium not only has the characteristics that luminous efficiency is high, chemical property is stable and is easily purified, and is applied as phosphorescent guest material and excellent luminous efficiency, electron mobility and stability are shown in organic electroluminescence device.By the modification of main part, the emission wavelength and efficiency of complex can be adjusted in visible light wave range.
Description
Technical field
The invention belongs to metal organic phosphorescent material and organic electroluminescent application field.It is more particularly to a kind of to be based on thiophene
Fen simultaneously phosphorescent iridium complex of [2,3-d] pyrimidine heterocyclic and preparation method thereof and uses such complex as phosphorescent guest material
Application in organic electroluminescence device.
Background technology
Organic electroluminescence device (Organic Light-Emitting Diodes, OLED) is due to brightness height, regarding
Angular width, fast response time, driving voltage are low, the advantages that being prepared available for large area flexible display, by academia and industry
The extensive concern on boundary, huge potentiality are shown in FPD of new generation and solid-state illumination etc..
According to the difference of principle of luminosity, electroluminescent organic material can be divided into the phosphor to be lighted based on singlet exciton
Material and the major class of phosphor material two based on Triplet exciton.In Organic Light Emitting Diodes, singlet exciton and three lines
State exciton produces simultaneously.According to spin quantum statistical theory, the generating probability ratio of singlet exciton and triplet excitons is 1:
3.For common organic electroluminescent fluorescent materials, only singlet exciton is luminous to be utilized, and triplet excitons mainly occur
Nonradiative transition loses, therefore the internal quantum efficiency of the maximum of the device based on common fluorescent material is 25%.But in phosphorus
In luminescent material heavy metal complex, due to the introducing of heavy metal atom, stronger spin(-)orbit coupling is produced between metal and part
Close, make excitation state triplet that there are some singlet state features, thus phosphor material can be swashed using singlet and triplet state simultaneously
Son, in theory the internal quantum efficiency of device can be made to reach 100%.Therefore, heavy metal complex is widely used in preparation
Efficient organic electroluminescence device.Wherein, complex of iridium is particularly important, because it has suitable triplet lifetime and height
Luminous efficiency, and the luminous of different wave length can be realized by the regulation to the first and second parts.
Phosphor material as electroluminescent device generally has longer lifetime of excited state, thus with seriously triple
State-triplet is quenched.Device maximal efficiency is typically occurred under low current density, with the increase of current density, efficiency and bright
Decay occurs in degree, limits application of the phosphor material in organic electroluminescence device.Therefore, exploitation have simultaneously it is high outer
Quantum efficiency and the phosphor material of low efficiency decay, have great importance.
It is an object of the invention to provide a kind of phosphorescent iridium complex with high-luminous-efficiency.These phosphorescent complexes are used
In the preparation of organic electroluminescence device, improve device efficiency and reduce device rate of decay.
The content of the invention
The purpose of the present invention aims to provide a kind of phosphorescent iridium complex with high-luminous-efficiency.
Second object of the present invention is to provide the preparation method of this kind of complex.
Third object of the present invention is that this kind of phosphor material is used in organic electroluminescence device, existing to solve
Electroluminescent device material efficiency it is low, roll-off the problem of fast.
Technical solution of the present invention is as follows：
A kind of novel metal complex of iridium, with thieno [2,3-d] pyrimidine heterocyclic derivative as main part, with levulinic
Ketone (acac), dipivaloylmethane (tmd) or 2- pyridine carboxylic acids (pic) are assistant ligand, and structure is shown below：
In the formula, L is selected from following group：
In the formula, Ar is selected from following group：
Wherein, R1、R2、R3And R4It is independently selected from following group：
-H、-NH2、-OCH3、-CH3、-C(CH3)3、-CN、-F、-CF3。
As some examples, the complex of iridium has one of following structure：
The method for preparing described phosphorescent iridium complex, comprises the following steps：
(1) under argon gas protection, 4- chlorothiophenes [2,3-d] pyrimidine and slight excess of boric acid A are added into Isosorbide-5-Nitrae-dioxy six
In ring, in Pd (dppf) Cl2Catalyst and 2M K2CO3(aq) effect is lower carries out Suzuki coupling reactions, after isolating and purifying
To the part B based on thiophene [2,3-d] pyrimidine heterocyclic.
Boric acid A structural formula is：
X-B(OH)2；
Part B structural formula is：
In the formula, X is selected from following group：
Wherein, R1、R2、R3And R4It is independently selected from following group：
-H、-NH2、-OCH3、-CH3、-C(CH3)3、-CN、-F、-CF3。
Reaction equation is as shown：
(2) it is 1 by mol ratio under argon gas protection：2.5 three hydrated iridium trichlorides and above-mentioned part B are dissolved in ethylene glycol
Ether and distilled water in the mixed solvent, react 24h at 120 DEG C, obtain chlorine bridge dimer intermediate., will without being further purified
Chlorine bridge dimer intermediate and acetylacetone,2,4-pentanedione, dipivaloylmethane or 2- pyridine carboxylic acids are dissolved in ethylene glycol ethyl ether, are added anhydrous
Sodium carbonate, react 12 hours at 80 DEG C.Isolate and purify to obtain target phosphorescent iridium complex.
Reaction equation is as follows：
The present invention also provides a kind of electro-phosphorescent luminescent device, including Conducting Glass layer, hole injection layer, hole biography
Defeated layer, luminescent layer, electron transfer layer, cathode layer；The luminescent material of luminescent layer is phosphorescent iridium complex of the present invention.
The phosphorescent guest material of the present invention is applied in electro phosphorescent device, can obtain efficient electroluminescent properties.This
The orange light electro phosphorescent device that invention is prepared using Ir-acac-01 as object, maximum luminous efficiency are often pacified up to 67.8 Kan Tela
Training, maximum lumen efficiency are 64.4 lumen per Watts, and maximum external quantum efficiency is 24.5%, while in 1000 every square of Kan Tela
Under rice, device has remained in that high stability, and external quantum efficiency remains at 24.3%.The present invention using Ir-tmd-22 as
Orange light electro phosphorescent device prepared by object, maximum luminous efficiency are up to 30.2 every ampere of Kan Tela, maximum lumen efficiency
36.4 lumen per Watts, maximum external quantum efficiency is 19.8%, while under 1000 every square metre of Kan Tela, device remains in that
High stability, external quantum efficiency remain at 19.2%.The present invention is electroluminescent as green glow prepared by object using Ir-pic-42
Phosphorescent devices, for maximum luminous efficiency up to 92.6 every ampere of Kan Tela, maximum lumen efficiency is 99.8 lumen per Watts, maximum outer
Quantum efficiency is 26.8%, while under 1000 every square metre of Kan Tela, device has remained in that high stability, outer quantum
Efficiency remains at 25.4%.As can be seen here, the present invention has beneficial technique effect.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of embodiment.
Fig. 2 is the phosphorescent iridium complex Ir-acac-01 of example 28 electroluminescent launching light spectrogram.
Fig. 3 is the phosphorescent iridium complex Ir-tmd-22 of example 30 electroluminescent launching light spectrogram.
Fig. 4 is the phosphorescent iridium complex Ir-pic-42 of example 32 electroluminescent launching light spectrogram.
Embodiment
The present invention provides a kind of phosphorescent organic compound and its application in organic electro-phosphorescent luminescent device.Lead to below
Instantiation is crossed to be described in further details the present invention, its object is to help to be better understood from present disclosure, purpose,
Technical scheme and effect, the raw material used in the present embodiment is known compound, is commercially available, several typical phosphorescence
Guest molecule can be synthesized with following methods：
Embodiment 1：Compound Ir-acac-01 preparation
The synthesis of 2- aminothiophene -3- carboxylate methyl esters (abbreviation intermediate 1)
The sulphur -2,5- of Isosorbide-5-Nitrae-two glycol (7.6g, 50mmol), malonic methyl ester nitrile are added in 250mL round-bottomed flasks
(9.9g, 100mmol) and 20mL DMF, by mixture in 0 DEG C of stirring.Triethylamine (3.6g, 50mmol) is gradually added dropwise to reaction
System, 3h is stirred at room temperature.Water quenching is added to go out, dichloromethane extraction, Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain
White solid (11g, 64%).
The synthesis of thiophene [2,3-d] pyrimidine -4- alcohol (abbreviation intermediate 2)
The addition 2- aminothiophene -3- carboxylate methyl esters (4.7g, 30mmol) in 250mL round-bottomed flasks, ammonium formate (6.3g,
100mmol) with 25mL formamides, by mixture, heating stirring reacts 6h at 150 DEG C.Reaction terminates to store 24h after 0 DEG C,
Filter, obtain brown solid (2.8g, 58%).
The synthesis of 4- chlorothiophenes [2,3-d] pyrimidine (abbreviation intermediate 3)
Thiophene [2,3-d] pyrimidine -4- alcohol (10.0g, 66mmol) and 100mL 1,4- bis- are added in 250mL round-bottomed flasks
The ring of oxygen six, by mixture in 0 DEG C of stirring.POCl3 (20mL, 212mmol) is gradually added dropwise to reaction system, by mixture in
Heating stirring reacts 3h at 90 DEG C.Room temperature is cooled to, reaction, dichloromethane extraction, rotary evaporation is quenched in sodium hydrate aqueous solution
Instrument removes solvent.Column chromatography purifies and separates.Obtain white solid (9.1g, 60%).
The synthesis of 4- tolylthiophenes [2,3-d] pyrimidine (abbreviation ligand L -01)
Under argon gas protection, phenyl boric acid (4.3g, 35mmol) is added in 250mL round-bottomed flasks, 4- chlorothiophenes [2,3-d] are phonetic
Pyridine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL Isosorbide-5-Nitraes-dioxy six
Ring and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane extraction, rotation
Evaporimeter removes solvent.Column chromatography purifies and separates.Obtain white solid (4.6g, 72%).
Target molecule Ir-acac-01 synthesis
Under argon gas protection, ligand L -01 (530mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (342mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (223mg, 31%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 714.04+]
Elementary analysis：C29H21IrN4O2S2
Theoretical value (%)：C 48.79,H 2.97,N 7.85
Actual value (%)：C 48.41,H 2.38,N 7.46
Embodiment 2：Compound Ir-acac-04 preparation
The synthesis of 4- (4- methoxyphenyls) thiophene [2,3-d] pyrimidines (abbreviation ligand L -04)
Under argon gas protection, 4- methoxyphenylboronic acids (5.3g, 35mmol), 4- chlorothiophenes are added in 250mL round-bottomed flasks
[2,3-d] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL 1,
4- dioxane and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane
Extraction, Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (5.4g, 74%).
Target molecule Ir-acac-04 synthesis
Under argon gas protection, ligand L -04 (605mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (412mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (248mg, 32%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 774.15+]
Elementary analysis：C31H25IrN4O2S2
Theoretical value (%)：C 48.11,H 3.26,N 7.24
Actual value (%)：C 48.05,H 3.28,N 7.33
Embodiment 3：Compound Ir-acac-06 preparation
The synthesis of 4- (4- aminomethyl phenyls) thiophene [2,3-d] pyrimidines (abbreviation ligand L -06)
Under argon gas protection, the addition 4- methylphenylboronic acids (4.8g, 35mmol) in 250mL round-bottomed flasks, 4- chlorothiophenes [2,
3-d] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL Isosorbide-5-Nitraes-
Dioxane and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane extraction
Take, Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (4.5g, 72%).
Target molecule Ir-acac-06 synthesis
Under argon gas protection, ligand L -06 (560mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (369mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (222mg, 30%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 742.05+]
Elementary analysis：C31H25IrN4O2S2
Theoretical value (%)：C 50.19,H 3.40,N 7.55
Actual value (%)：C 50.15,H 3.42,N 7.48
Embodiment 4：Compound Ir-acac-09 preparation
The synthesis of 4- (4- cyano-phenyls) thiophene [2,3-d] pyrimidines (abbreviation ligand L -09)
Under argon gas protection, the addition 4- cyanophenylboronic acids (5.2g, 35mmol) in 250mL round-bottomed flasks, 4- chlorothiophenes [2,
3-d] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL Isosorbide-5-Nitraes-
Dioxane and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane extraction
Take, Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (4.8g, 68%).
Target molecule Ir-acac-09 synthesis
Under argon gas protection, ligand L -09 (593mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (382mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (267mg, 35%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 764.06+]
Elementary analysis：C31H19IrN6O2S2
Theoretical value (%)：C 48.74,H 2.51,N 11.00
Actual value (%)：C 48.68,H 2.53,N 11.02
Embodiment 5：Compound Ir-acac-12 preparation
The synthesis of 4- (2,4 difluorobenzene base) thiophene [2,3-d] pyrimidines (abbreviation ligand L -12)
Under argon gas protection, 2,4- difluoros phenyl boric acid (5.9g, 35mmol), 4- chlorothiophenes are added in 250mL round-bottomed flasks
[2,3-d] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL 1,
4- dioxane and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane
Extraction, Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (6.1g, 82%).
Target molecule Ir-acac-12 synthesis
Under argon gas protection, ligand L -12 (620mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (397mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (282mg, 36%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 786.04+]
Elementary analysis：C29H17IrN4O2S2
Theoretical value (%)：C 44.33,H 2.18,N 7.13
Actual value (%)：C 44.28,H 2.15,N 7.18
Embodiment 6：Compound Ir-acac-15 preparation
The synthesis of 4- (trifluoromethyls of 2,4- bis-) thiophene [2,3-d] pyrimidines (abbreviation ligand L -15)
Under argon gas protection, the trifluoromethylbenzene boronic acids of 2,4- bis- (9.0g, 35mmol), 4- are added in 250mL round-bottomed flasks
Chlorothiophene [2,3-d] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol),
60mL Isosorbide-5-Nitraes-dioxane and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, two
Chloromethanes extracts, and Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (8.6g, 83%).
Target molecule Ir-acac-15 synthesis
Under argon gas protection, ligand L -15 (870mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (415mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (325mg, 33%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 986.02+]
Elementary analysis：C33H17F12IrN4O2S2
Theoretical value (%)：C 40.21,H 1.74,N 5.68
Actual value (%)：C 40.25,H 1.82,N 5.63
Embodiment 7：Compound Ir-tmd-16 preparation
Under argon gas protection, ligand L -16 (530mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (402mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (255mg, 32%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 798.17+]
Elementary analysis：C35H33IrN4O2S2
Theoretical value (%)：C 52.68,H 4.17,N 7.02
Actual value (%)：C 52.61,H 4.19,N 6.95
Embodiment 8：Compound Ir-tmd-19 preparation
Under argon gas protection, ligand L -19 (605mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (416mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (308mg, 36%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 858.19+]
Elementary analysis：C37H37IrN4O4S2
Theoretical value (%)：C 51.79,H 4.35,N 6.53
Actual value (%)：C 51.85,H 4.42,N 6.48
Embodiment 9：Compound Ir-tmd-21 preparation
Under argon gas protection, ligand L -21 (510mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (416mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (308mg, 36%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 841.22+]
Elementary analysis：C38H40IrN4O2S2
Theoretical value (%)：C 54.26,H 4.79,N 6.66
Actual value (%)：C 54.31,H 4.75,N 6.49
Embodiment 10：Compound Ir-tmd-24 preparation
Under argon gas protection, ligand L -24 (592mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (416mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (271mg, 32%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 848.17+]
Elementary analysis：C37H31IrN6O2S2
Theoretical value (%)：C 52.40,H 3.68,N 9.91
Actual value (%)：C 52.45,H 3.72,N 9.85
Embodiment 11：Compound Ir-tmd-27 preparation
Under argon gas protection, ligand L -27 (620mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (450mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (321mg, 37%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 870.15+]
Elementary analysis：C35H29F4IrN4O2S2
Theoretical value (%)：C 48.32,H 3.36,N 6.44
Actual value (%)：C 48.39,H 3.31,N 6.45
Embodiment 12：Compound Ir-tmd-30 preparation
Under argon gas protection, ligand L -30 (678mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (569mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (385mg, 37%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 1070.15+]
Elementary analysis：C39H29F12IrN4O2S2
Theoretical value (%)：C 43.78,H 2.73,N 5.24
Actual value (%)：C 43.73,H 2.71,N 5.21
Embodiment 13：Compound Ir-pic-31 preparation
Under argon gas protection, ligand L -31 (530mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (447mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (309mg, 42%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 736.98+]
Elementary analysis：C30H18IrN5O2S2
Theoretical value (%)：C 48.90,H 2.46,N 9.50
Actual value (%)：C 48.95,H 2.41,N 9.46
Embodiment 14：Compound Ir-pic-34 preparation
Under argon gas protection, ligand L -34 (605mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (512mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (358mg, 45%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 797.05+]
Elementary analysis：C32H22IrN5O4S2
Theoretical value (%)：C 48.23,H 2.78,N 8.79
Actual value (%)：C 48.19,H 2.71,N 8.75
Embodiment 15：Compound Ir-pic-36 preparation
Under argon gas protection, ligand L -36 (565mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (475mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (320mg, 41%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 781.15+]
Elementary analysis：C33H26IrN5O2S2
Theoretical value (%)：C 50.75,H 3.36,N 8.97
Actual value (%)：C 50.67,H 3.41,N 8.95
Embodiment 16：Compound Ir-pic-39 preparation
Under argon gas protection, ligand L -39 (592mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (488mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (370mg, 47%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 787.01+]
Elementary analysis：C32H16IrN7O2S2
Theoretical value (%)：C 48.85,H 2.05,N 12.46
Actual value (%)：C 48.81,H 2.08,N 12.44
Embodiment 17：Compound Ir-pic-42 preparation
Under argon gas protection, ligand L -42 (600mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (460mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (223mg, 30%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 824.02+]
Elementary analysis：C31H17F4IrN5O2S2
Theoretical value (%)：C 45.20,H 2.08,N 9.22
Actual value (%)：C 45.48,H 2.25,N 9.14
Embodiment 18：Compound Ir-pic-45 preparation
Under argon gas protection, ligand L -45 (870mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (610mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (464mg, 46%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 1009.00+]
Elementary analysis：C34H14F12IrN5O2S2
Theoretical value (%)：C 40.48,H 1.40,N 6.94
Actual value (%)：C 40.45,H 1.38,N 6.99
Embodiment 19：Compound Ir-acac-47 preparation
The synthesis of 4- (4- pyridines) thiophene [2,3-d] pyrimidines (abbreviation ligand L -47)
Under argon gas protection, 4- pyridine boronic acids (4.3g, 35mmol), 4- chlorothiophenes [2,3- are added in 250mL round-bottomed flasks
D] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL Isosorbide-5-Nitraes-two
The ring of oxygen six and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane extraction,
Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (4.6g, 72%).
Target molecule Ir-acac-47 synthesis
Under argon gas protection, ligand L -47 (532mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (366mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (344mg, 48%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 716.03+]
Elementary analysis：C27H19IrN6O2S2
Theoretical value (%)：C 45.30,H 2.68,N 11.74
Actual value (%)：C 45.26,H 2.61,N 11.69
Embodiment 20：Compound Ir-acac-49 preparation
The synthesis of 4- (2- naphthyls) thiophene [2,3-d] pyrimidines (abbreviation ligand L -49)
Under argon gas protection, 4- naphthalenylboronic acids (6.0g, 35mmol), 4- chlorothiophenes [2,3- are added in 250mL round-bottomed flasks
D] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL Isosorbide-5-Nitraes-two
The ring of oxygen six and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane extraction,
Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (5.9g, 75%).
Target molecule Ir-acac-49 synthesis
Under argon gas protection, ligand L -49 (655mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (374mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (333mg, 41%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 814.05+]
Elementary analysis：C37H25IrN4O2S2
Theoretical value (%)：C 54.60,H 3.10,N 6.88
Actual value (%)：C 54.57,H 3.05,N 6.83
Embodiment 21：Compound Ir-acac-50 preparation
The synthesis of 4- (2- furans) thiophene [2,3-d] pyrimidines (abbreviation ligand L -50)
Under argon gas protection, 2- furan boronic acids (3.9g, 35mmol), 4- chlorothiophenes [2,3- are added in 250mL round-bottomed flasks
D] pyrimidine (5.1g, 30mmol), Pd (dppf) Cl2(440mg, 0.6mmol), K2CO3(5.5g, 40mmol), 60mL Isosorbide-5-Nitraes-two
The ring of oxygen six and 20mL water, mixture is reacted into 6h in 90 DEG C of heating stirrings.Room temperature is cooled to, adds water quenching to go out, dichloromethane extraction,
Rotary Evaporators remove solvent.Column chromatography purifies and separates.Obtain white solid (4.5g, 75%).
Target molecule Ir-acac-50 synthesis
Under argon gas protection, ligand L -50 (505mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (356mg,
0.4mmol), acetylacetone,2,4-pentanedione (200mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.React on
80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic phase,
Anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (326mg, 47%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 694.01+]
Elementary analysis：C25H17IrN4O4S2
Theoretical value (%)：C 43.28,H 2.47,N 8.08
Actual value (%)：C 43.25,H 2.55,N 8.17
Embodiment 22：Compound Ir-tmd-55 preparation
Under argon gas protection, ligand L -55 (532mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (416mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (256mg, 32%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 800.12+]
Elementary analysis：C33H31IrN6O2S2
Theoretical value (%)：C 49.55,H 3.91,N 10.51
Actual value (%)：C 49.52,H 3.93,N 10.48
Embodiment 23：Compound Ir-tmd-57 preparation
Under argon gas protection, ligand L -57 (655mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (587mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (341mg, 38%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 898.15+]
Elementary analysis：C43H37IrN4O2S2
Theoretical value (%)：C 57.51,H 4.15,N 6.24
Actual value (%)：C 57.44,H 4.12,N 6.33
Embodiment 24：Compound Ir-tmd-58 preparation
Under argon gas protection, ligand L -58 (505mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (556mg,
0.4mmol), dipivaloylmethane (246mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Instead
It should be carried out 12 hours under the conditions of argon atmosphere in 80 DEG C.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (256mg, 33%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 778.07+]
Elementary analysis：C31H29IrN4O4S2
Theoretical value (%)：C 47.86,H 3.76,N 7.20
Actual value (%)：C 47.81,H 3.72,N 7.25
Embodiment 25：Compound Ir-pic-63 preparation
Under argon gas protection, ligand L -63 (592mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (488mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (273mg, 37%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 739.02+]
Elementary analysis：C28H16IrN7O2S2
Theoretical value (%)：C 45.52,H 2.18,N 13.27
Actual value (%)：C 45.55,H 2.12,N 13.25
Embodiment 26：Compound Ir-pic-65 preparation
Under argon gas protection, ligand L -65 (655mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (695mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (352mg, 42%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 837.09+]
Elementary analysis：C38H22IrN5O2S2
Theoretical value (%)：C 54.53,H 2.65,N 8.37
Actual value (%)：C 54.48,H 2.62,N 8.31
Embodiment 27：Compound Ir-pic-66 preparation
Under argon gas protection, ligand L -66 (505mg, 2.5mmol), iridous chloride (three are added in 100mL round-bottomed flasks
The crystallization water) (350mg, 1mmol), 15mL ethylene glycol ethyl ethers and 5mL distilled water.24h is carried out under the conditions of reacting on 120 DEG C.Cooling
To room temperature, it is poured into water.Filtering precipitate.Water, ethanol, ether washing are used respectively.Vacuum drying.Obtain among chlorine bridge polymers
Body, orange solids.Without being further purified, be separately added into 100mL round-bottomed flasks chlorine bridge polymers intermediate (587mg,
0.4mmol), 2- pyridine carboxylic acids (368mg, 2mmol), natrium carbonicum calcinatum (210mg, 2mmol) and 10mL ethylene glycol ethyl ethers.Reaction
In 80 DEG C, carried out 12 hours under the conditions of argon atmosphere.After being cooled to room temperature, add water quenching to go out, dichloromethane extraction, merge organic
Phase, anhydrous sodium sulfate drying, filtering.Silica gel column chromatography separates.Obtain orange solids (322mg, 45%).
Structural Identification：
[the M of mass spectrum (EI, m/z) 717.05+]
Elementary analysis：C26H14IrN5O2S2
Theoretical value (%)：C 43.57,H 1.97,N 9.77
Actual value (%)：C 43.52,H 1.93,N 9.72
Embodiment 28：The preparation of the phosphorescent organic electroluminescent device of the Ir-acac-01 containing complex
Ito glass is cleaned 30 minutes in cleaning agent and deionized water with ultrasonic wave in succession, is dried in vacuo 2 hours, then
Ito glass is done into ozone plasma processing in 5 minutes, organic film and metal electrode are then prepared in vacuum glove box.Such as Fig. 1
It is shown, the electro phosphorescent device of phosphor material of the invention as luminescent layer.It may include glass and electro-conductive glass (ITO) substrate layer
1, (the molybdenum trioxide MoO of hole injection layer 23), hole transmission layer 3 (4,4 '-cyclohexyl two [N, N- bis- (4- aminomethyl phenyls) aniline]
TAPC), luminescent layer 4 (mixture of phosphorescent guest material Ir-acac-01 incorporations material of main part of the present invention), electron transfer layer 5
(4,7- diphenyl -1,10- ferrosin Bphen), cathode layer 6 (lithium fluoride/aluminium LiF/Al).
Current versus brightness-voltage characteristic of device is measured by the Keithley sources with corrected silicon photoelectric diode
What system (Keithley 2400Sourcemeter, Keithley 2000Currentmeter) was completed, electroluminescent spectrum is
By French JY companies SPEX CCD3000 spectrometer measurements, all measurements are completed in atmosphere at room temperature.
Device 1 (D1) structure is：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-acac-01 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The orange light electro phosphorescent device that the present invention is prepared using Ir-acac-01 as object, maximum luminous efficiency is up to 67.8 banks
Every ampere of Te La, maximum lumen efficiency are 64.4 lumen per Watts, and maximum external quantum efficiency is 24.5%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 24.3%.
Embodiment 29：The preparation of the phosphorescent organic electroluminescent device of the Ir-acac-06 containing complex
Except the phosphorescent guest material of luminescent layer is changed into Ir-acac-06, other application makes with the same method of example 28 to be had
Organic electroluminescence devices.
Device 2 (D2) structure：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-acac-06 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The orange light electro phosphorescent device that the present invention is prepared using Ir-acac-06 as object, maximum luminous efficiency is up to 31.3 banks
Every ampere of Te La, maximum lumen efficiency are 37.8 lumen per Watts, and maximum external quantum efficiency is 20.1%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 19.8%.
Embodiment 30：The preparation of the phosphorescent organic electroluminescent device of the Ir-tmd-22 containing complex
Except the phosphorescent guest material of luminescent layer is changed into Ir-tmd-22, other application makes with the same method of example 28 to be had
Organic electroluminescence devices.
Device 3 (D3) structure：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-tmd-22 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The orange light electro phosphorescent device that the present invention is prepared using Ir-tmd-22 as object, maximum luminous efficiency is up to 30.2 banks
Every ampere of Te La, maximum lumen efficiency are 36.4 lumen per Watts, and maximum external quantum efficiency is 19.8%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 19.2%.
Embodiment 31：The preparation of the phosphorescent organic electroluminescent device of the Ir-tmd-30 containing complex
Except the phosphorescent guest material of luminescent layer is changed into Ir-tmd-30, other application makes with the same method of example 28 to be had
Organic electroluminescence devices.
Device 4 (D4) structure：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-tmd-30 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The orange light electro phosphorescent device that the present invention is prepared using Ir-tmd-30 as object, maximum luminous efficiency is up to 34.1 banks
Every ampere of Te La, maximum lumen efficiency are 38.5 lumen per Watts, and maximum external quantum efficiency is 24.2%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 22.3%.
Embodiment 32：The preparation of the phosphorescent organic electroluminescent device of the Ir-pic-42 containing complex
Except the phosphorescent guest material of luminescent layer is changed into Ir-pic-42, other application makes with the same method of example 28 to be had
Organic electroluminescence devices.
Device 5 (D5) structure：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-pic-42 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The green glow electro phosphorescent device that the present invention is prepared using Ir-pic-42 as object, maximum luminous efficiency is up to 92.6 banks
Every ampere of Te La, maximum lumen efficiency are 99.8 lumen per Watts, and maximum external quantum efficiency is 26.8%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 25.4%.
Embodiment 33：The preparation of the phosphorescent organic electroluminescent device of the Ir-pic-45 containing complex
Except the phosphorescent guest material of luminescent layer is changed into Ir-pic-45, other application makes with the same method of example 28 to be had
Organic electroluminescence devices.
Device 6 (D6) structure：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-pic-45 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The green glow electro phosphorescent device that the present invention is prepared using Ir-pic-45 as object, maximum luminous efficiency is up to 89.3 banks
Every ampere of Te La, maximum lumen efficiency are 85.1 lumen per Watts, and maximum external quantum efficiency is 23.5%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 20.5%.
Embodiment 34：The preparation of the phosphorescent organic electroluminescent device of the Ir-tmd-57 containing complex
Except the phosphorescent guest material of luminescent layer is changed into Ir-tmd-57, other application makes with the same method of example 28 to be had
Organic electroluminescence devices.
Device 7 (D7) structure：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-tmd-57 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The green glow electro phosphorescent device that the present invention is prepared using Ir-tmd-57 as object, maximum luminous efficiency is up to 34.4 banks
Every ampere of Te La, maximum lumen efficiency are 36.7 lumen per Watts, and maximum external quantum efficiency is 22.9%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 19.8%.
Embodiment 35：The preparation of the phosphorescent organic electroluminescent device of the Ir-pic-68 containing complex
Except the phosphorescent guest material of luminescent layer is changed into Ir-pic-68, other application makes with the same method of example 28 to be had
Organic electroluminescence devices.
Device 8 (D8) structure：
ITO/MoO3(8nm)/TAPC(75nm)/NPB:Ir-pic-68 (5wt%, 12nm)/Bphen (70nm)/LiF
(1nm)/Al(150nm)
The green glow electro phosphorescent device that the present invention is prepared using Ir-pic-68 as object, maximum luminous efficiency is up to 38.5 banks
Every ampere of Te La, maximum lumen efficiency are 40.2 lumen per Watts, and maximum external quantum efficiency is 26.5%, while in 1000 Kan Te
Draw under every square metre, device has remained in that high stability, and external quantum efficiency remains at 22.7%.
The above embodiment of the present invention is only to illustrate example of the present invention to be clear, not embodiments of the present invention
Restriction.For the person of ordinary skill of the art, other multi-forms can also be made on the basis of the above description
Change or variation, all embodiments can not be enumerated herein.Every technical scheme that belongs to is drawn
Row of the obvious changes or variations that Shen goes out still in protection scope of the present invention.
Claims (4)
- A 1. metal iridium complexes, it is characterised in that with thieno [2,3-d] pyrimidine heterocyclic derivative as main part, with Acetylacetone,2,4-pentanedione, dipivaloylmethane or 2- pyridine carboxylic acids are assistant ligand, and structure is shown below：In the formula, L is selected from following group：In the formula, Ar is selected from following group：Wherein, R1、R2、R3And R4It is independently selected from following group：‐H、‐NH2、‐OCH3、‐CH3、‐C(CH3)3、‐CN、‐F、‐CF3。
- 2. complex of iridium according to claim 1, it is characterised in that the complex of iridium has one of following structure：
- A kind of 3. method for preparing phosphorescent iridium complex as claimed in claim 1, it is characterised in that：Synthetic method includes as follows Step：(1) under argon gas protection, 4- chlorothiophenes [2,3-d] pyrimidine and excessive boric acid A are added in Isosorbide-5-Nitrae-dioxane, in Pd (dppf)Cl2Catalyst and 2M K2CO3(aq) Suzuki coupling reactions are carried out under catalytic action, are based on after isolating and purifying The part B of thiophene [2,3-d] pyrimidine heterocyclic；(2) it is 1 by mol ratio under argon gas protection：2.5 three hydrated iridium trichlorides and above-mentioned part B are dissolved in ethylene glycol ethyl ether With distilled water in the mixed solvent, 24h is reacted at 120 DEG C, obtains chlorine bridge dimer intermediate；Without being further purified, by chlorine bridge Dimer intermediate and acetylacetone,2,4-pentanedione, dipivaloylmethane or 2- pyridine carboxylic acids are dissolved in ethylene glycol ethyl ether, add Carbon Dioxide Sodium, react 12 hours at 80 DEG C, isolate and purify to obtain target phosphorescent iridium complex；Boric acid A structural formula is：X-B(OH)2；Part B structural formula is：In the formula, X is selected from following group：Wherein, R1、R2、R3And R4It is independently selected from following group：‐H、‐NH2、‐OCH3、‐CH3、‐C(CH3)3、‐CN、‐F、‐CF3。
- 4. a kind of electro-phosphorescent luminescent device, including Conducting Glass layer, hole injection layer, hole transmission layer, luminescent layer, electricity Sub- transport layer, cathode layer；It is characterized in that：The luminescent material of luminescent layer is that the phosphorescent iridium described in the claims in the present invention 1 or 2 is matched somebody with somebody Compound.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111362986A (en) * | 2020-04-23 | 2020-07-03 | 安徽工业大学 | Thieno [2,3-d ] pyridazine cyclometalated iridium complex and preparation method thereof |
| US11377458B2 (en) * | 2017-10-16 | 2022-07-05 | Samsung Electronics Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
| EP4001287B1 (en) * | 2020-11-24 | 2024-01-17 | Universal Display Corporation | Organic electroluminescent materials and devices |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060134462A1 (en) * | 2004-12-22 | 2006-06-22 | Industrial Technology Research Institute | Organometallic complex and organic electroluminescent devices utilizing the same |
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2017
- 2017-08-30 CN CN201710766053.8A patent/CN107573386A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060134462A1 (en) * | 2004-12-22 | 2006-06-22 | Industrial Technology Research Institute | Organometallic complex and organic electroluminescent devices utilizing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11377458B2 (en) * | 2017-10-16 | 2022-07-05 | Samsung Electronics Co., Ltd. | Organometallic compound and organic light-emitting device including the same |
| CN111362986A (en) * | 2020-04-23 | 2020-07-03 | 安徽工业大学 | Thieno [2,3-d ] pyridazine cyclometalated iridium complex and preparation method thereof |
| CN111362986B (en) * | 2020-04-23 | 2023-04-07 | 安徽工业大学 | Thieno [2,3-d ] pyridazine cyclometalated iridium complex and preparation method thereof |
| EP4001287B1 (en) * | 2020-11-24 | 2024-01-17 | Universal Display Corporation | Organic electroluminescent materials and devices |
| EP4329463A3 (en) * | 2020-11-24 | 2024-05-29 | Universal Display Corporation | Organic electroluminescent materials and devices |
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Application publication date: 20180112 |