CN107973823A - The electroluminescent organic material of a kind of quinolyl dibenzo substitution as ligand and application thereof - Google Patents

The electroluminescent organic material of a kind of quinolyl dibenzo substitution as ligand and application thereof Download PDF

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CN107973823A
CN107973823A CN201610918184.9A CN201610918184A CN107973823A CN 107973823 A CN107973823 A CN 107973823A CN 201610918184 A CN201610918184 A CN 201610918184A CN 107973823 A CN107973823 A CN 107973823A
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鄢亮亮
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EverDisplay Optronics Shanghai Co Ltd
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Abstract

It is a kind of that compound of ligand and application thereof is used as using the substitution of quinolyl dibenzo.The compound has structure shown in Formulas I.Compound provided by the invention has the advantages that heat endurance is good, and luminous efficiency is high, long lifespan, can be used in organic luminescent device, especially as emitting red light doping body, has the possibility applied to AMOLED industries.

Description

Organic electroluminescent material with quinolyl dibenzo substitution as ligand and application thereof
Technical Field
The invention belongs to the field of electroluminescent materials, and particularly relates to an organic electroluminescent material taking quinolyl dibenzo substitution as a ligand and application thereof.
Background
The organic electroluminescence refers to a phenomenon that a thin film device prepared from an organic photoelectric functional material emits light under the excitation action of a field. The organic electroluminescent diode (OLED) and the polymer electroluminescent diode (PLED) may be classified according to the luminescent material used to prepare the functional thin film.
The OLED as a brand new display technology has the advantages that the existing display technology has no ethical ratio in all performances, such as full solid state, self-luminescence, high brightness, high resolution, wide viewing angle (more than 170 degrees), high response speed, thin thickness, small volume, light weight, capability of using a flexible substrate, low-voltage direct current driving (3-10V), low power consumption, wide working temperature range and the like, so that the OLED has a wide application market, such as an illumination system, a communication system, vehicle-mounted display, portable electronic equipment, high-definition display and even the military field.
The light emitting process of the OLED device is as follows, (1) injection of carriers: under the action of an external electric field, electrons and holes are respectively injected into the organic functional thin film layer clamped between the electrodes from the cathode and the anode; (2) migration of carriers: the injected electrons and holes respectively migrate from the electron transport layer and the hole transport layer to the light emitting layer; (3) recombination of carriers: the electrons and holes combine to generate excitons; (4) transfer of excitons: the excitons migrate under the action of an electric field, transfer energy to optical molecules, and excite electrons to transition from a ground state to an excited state; (5) electroluminescence: the excited state energy is deactivated by radiation, producing photons, releasing energy. When electrons and holes recombine in an organic molecule, two excited states, one approximately 25% singlet and one 75% triplet, are produced due to the difference in the electron spin symmetry.
The organic electroluminescent material is a core component of an organic electroluminescent device, and the thermal stability, photochemical stability, quantum efficiency, film forming property, crystallinity and the like of the material have great influence on the performance of the manufactured device, and can comprise fluorescent materials and phosphorescent materials.
It is generally believed that the fluorescent material is typically an organic small molecule material with a limit of 25% internal quantum efficiency, as CN105418582A discloses a high fluorescent material comprising a single (n ═ 0) or a series of (n ═ 1, 2, etc.) benzo-heterocycle systems. The phosphorescent material can utilize 75% of energy of triplet excitons due to spin-orbit coupling caused by the heavy atom effect, so that the luminous efficiency is improved without any problem. Compared with fluorescent materials, phosphorescent materials not only start late, but also have the problems of poor thermal stability, low luminous efficiency, short service life, low color saturation and the like, and are a very challenging problem up to now.
Disclosure of Invention
One of the objectives of the present invention is to provide a new compound of a heteroleptic complex with a quinolinyl dibenzo substituent as a ligand, which has the advantages of good thermal stability, high light-emitting efficiency, long lifetime, etc., and can be used in organic light-emitting devices, particularly as a red light-emitting dopant, with the possibility of being applied to AMOLED industry.
In order to achieve the purpose, the invention adopts the following technical scheme:
a compound using quinolyl dibenzo substitution as a ligand has a structure shown in formula I:
wherein,
z is selected from O, S, CR2, NR or Se, wherein R is alkyl, heteroalkyl, aryl or heteroaryl, and the like;
R1，R2，R3，R4each independently selected from hydrogen, alkyl, heteroalkyl, aryl or heteroaryl;
m is a metal;
X-Y is a monoanionic bidentate ligand;
the sum of a and b is the valence of the metal ion.
Preferably, the compound has the following formula II:
preferably, R1，R2，R3Each independently is hydrogen, mono-, di-or poly-substituted, preferably mono-substituted.
Preferably, R4Independently hydrogen or mono-or di-or polysubstituted, preferably hydrogen.
Preferably, R1，R2Independently a substituent or a fused ring structure with the parent.
Preferably, R1，R2，R3Independently an electron donating alkyl or heteroalkyl group of no more than four carbon atoms, preferably an electron donating branched alkyl group containing no more than 4 carbon atoms.
Preferably, R3The substitution position of (b) is an adjacent position of a metal-carbon bond.
Preferably, R3The substitution position of (b) is the relative position of the metal-carbon bond.
Preferably, M is a metal having an atomic coefficient of greater than 40, preferably Cu, Pt, Pd, Os, or Ir, more preferably Pt or Ir, and particularly preferably Ir.
X-Y may be the same as or different from the ligand on the left, and preferably X-Y is different from the ligand on the left. When X-Y is different from the main ligand on the left, X-Y is preferably of a 1, 3-diketone structure.
Preferably, the compound is of the structure:
preferably, the compound is of the structure:
it is also an object of the present invention to provide an OLED phosphorescent guest material comprising the above compound.
It is also an object of the present invention to provide an OLED device comprising the above-mentioned compound.
The material of the invention not only has higher luminous efficiency, but also has more saturated red color codes, and meanwhile, the service life of the device is longer. The metal complex of the present invention can convert triplet excitation energy into light as a guest material, and therefore, can be applied to display devices such as organic electroluminescence devices, and can improve the light emission efficiency of the devices, thereby reducing energy consumption. Meanwhile, the complex has the advantages of good stability, long service life, high color saturation and the like, and has good application prospect in the display device industries such as OLED and the like.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The raw materials, acid-base catalysts and solvents involved in the synthesis of the compounds of the present invention are available from suppliers well known to those skilled in the art, such as carbofuran technology, Sigma, etc.
Example (b):
common intermediate synthesis as shown in the following 3:
synthesis of Compound 2:
compound 1(25.44g, 0.12mol, 1.2eq), 2-chloroquine (16.3g, 0.1mol, 1.0eq), Cs2CO3(97.5g, 0.3mol, 3.0eq), and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged in a 3L round bottom flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Then cooled to room temperature, concentrated under vacuum using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of saturated aqueous sodium carbonate solution were slowly added, stirred, the layers were separated, and the organic phase was successively diluted with saturated sodium carbonate (300 ml. times.3), H2Washing with O (300ml of 3) and saturated sodium chloride (300ml of 3), drying with sodium sulfate, filtering, concentrating the filtrate in vacuo using a rotary evaporator to remove the organic solvent and obtain the crude product, and adding acetic acidThe crude product was purified by column chromatography using ethyl ester/petroleum ether (volume ratio 1:2) as the mobile phase and dried under vacuum at 50 ℃ to give compound 2(25.5g, yield: 86.44%).
As a result:
yield: 86.44 percent.
MS:m/z＝296.1(M+H+)；1HNMR(400M，d6-DMSO):8.06(dd，1H)，7.93(dd，1H)，7.62-7.73(m，3H)，7.42-7.51(m，5H)，7.14-7.25(m，3H).Anal.Calcd for C21H13NO:C，85.40；H，4.44；N，4.74.Found:C，85.39；H，4.45；N，4.73。
Synthesis of Compound 3:
2- (4-Dibenzofuranyl) quinoline (Compound 2) (8.85g, 0.03mol, 3.0eq) and iridium trichloride trihydrate (3.52g, 0.01mol, 1.0eq) were placed in a three-necked flask, 2-ethoxyethanol (66.7ml) and deionized water (33.3ml) were added, and the resulting mixture was reacted for 16hrs under nitrogen protection at about 110 ℃. Cooled to room temperature, filtered, and the filtrate was skimmed off, and the residue was dried with methanol (50 ml. times.3) and n-hexane (50 ml. times.3) in this order to give Compound 3(5.45g, yield: 66.75%) as a gray solid. The obtained compound 3 was used in the next step without purification.
Example 1 synthesis of compound CPD 1:
the dichloro bridge complex compound 3(4.08g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and acetylacetone (2.5g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the reaction was carried out at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 1. (2.03g, yield: 46.1%).
Results of CPD1 yield: 46.1 percent. MS M/z 881.2(M + H +).
Example 2 synthesis of compound CPD 2:
the dichloro bridge complex compound 3(4.08g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2, 8-dimethylnonane-4, 6-dione (4.6g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the mixture was reacted at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. Adding 1g of C salt and 200ml of dichloromethane into the reaction solution to dissolve the product, then filtering the mixed solution through a C salt bed, filtering the filtrate through a short silica gel column to obtain a filtrate, removing most of dichloromethane, adding 30ml of isopropanol into the filtrate to precipitate a red solid, and filtering. The solid is separated by column chromatography to obtain the target complex CPD 2. (1.98g, yield: 41.1%).
Results of CPD2 yield: 41.1 percent. MS M/z 965.3(M + H +).
Example 3 synthesis of compound CPD 3:
the dichloro bridge complex compound 3(4.08g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2-acetylphenol (3.4g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the mixture was reacted at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 3. (1.58g, yield: 34.5%).
Results of CPD3 yield: 34.5 percent. MS M/z 917.2(M + H +).
Example 4 synthesis of compound CPD 4:
the first step is as follows: synthesis of triflate
Dimer compound 3(32.64g, 0.02mol, 1.0eq) was dissolved in 1L of dichloromethane, to which was added silver trifluoromethanesulfonate (10.5g, 0.04mol, 2.0eq) and isopropanol (75ml) in that order. The mixture was stirred at room temperature overnight. The silver chloride was filtered off and the filtrate was spin dried to give 41g of product, which was used directly in the next reaction without purification.
The second step is that: synthesis of Compound CPD4
The product of the first step (21.0g, 0.02mol, 1.0eq) and 2-phenylpyridine (9.3g, 0.06mol, 3.0eq) were dissolved in 200ml of anhydrous ethanol, and the mixture was heated under reflux overnight under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, the precipitate was filtered and washed with methanol and n-hexane in sequence for 3 times. After drying at 50 ℃ in vacuo, the title compound CPD4(14.6g, yield 78.1%) was obtained. The dried CPD4 was used directly for sublimation purification to give the pure objective compound CPD4(10.1g, 69.18% yield) as a sublimated product.
Synthesis of common intermediates as shown in the following 9:
synthesis of Compound 6
Compound 5(24.59g, 0.1mol, 1.0eq), trimethylcyclotriboroxane (15.1g, 0.12mol, 1.2eq), Cs2CO3(97.5g, 0.3mol, 3.0eq), and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged in a 3L round bottom flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Subsequently, the mixture was cooled to room temperature, concentrated under vacuum using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of a saturated aqueous solution of sodium carbonate was slowly added, stirred, and the layers were separated, the organic phase was washed with saturated sodium carbonate (300 ml. times.3), H2O (300 ml. times.3), and saturated sodium chloride (300 ml. times.3) in this order, dried over sodium sulfate and filtered, the filtrate was concentrated under vacuum using a rotary evaporator to remove the organic solvent and obtain a crude product, and the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:5) as a mobile phase, and dried under vacuum at 50 ℃ to obtain Compound 6(14.7g, yield: 80.77%).
As a result:
yield: 80.77 percent.
MS:m/z＝183.1(M+H+)；1HNMR(400M，d6-DMSO):7.49(d，1H)，7.4(dd，1H)，7.28-7.30(m，2H)，6.99-7.2(m，3H)，2.35(s，3H).Anal.Calcd for C13H10O:C，85.69；H，5.53.Found:C，85.68；H，5.54。
Synthesis of Compound 7
In a 2L three-necked flask, compound 6(18.2g, 0.1mol, 1.0eq) was dissolved in 225ml of anhydrous tetrahydrofuran, the reaction solution was cooled to-78 ℃ under nitrogen protection, 125ml (0.2mol) of a 1.6mol/L solution of BuLi in hexane was slowly added to the mixture, and the mixture was stirred at-78 ℃ for 30min under nitrogen protection. After naturally returning to room temperature, the reaction was stirred overnight. The reaction mixture was cooled again to-78 ℃ and 33.75ml (0.3mol, 3.0eq) of trimethyl borate was slowly added and stirred at room temperature for 4 hours. 800ml of 1mol/L HCl solution are slowly added and stirring is continued for 1 hour. Vacuum concentration was performed using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 300ml of saturated aqueous sodium carbonate solution was slowly added, stirring was performed, the layers were separated, the organic phase was washed with saturated sodium carbonate (300 ml. times.2), H2O (300 ml. times.3) and saturated sodium chloride (300 ml. times.3) in this order, dried over sodium sulfate and filtered, the filtrate was vacuum concentrated using a rotary evaporator to remove the organic solvent and obtain a crude product, the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:5) as a mobile phase, and dried under vacuum at 50 ℃ to obtain Compound 7(17.8g, yield: 78.77%).
As a result:
yield: 78.77 percent.
MS:m/z＝227.1(M+H+)；1HNMR(400M，d6-DMSO):7.49(dd，1H)，7.4(dd，1H)，7.28-7.30(m，4H)，2.32(s，3H).Anal.Calcd for C13H11BO3:C，69.08；H，4.91.Found:C，69.08；H，4.91。
Synthesis of Compound 8
Compound 7(27.12g, 0.12mol, 1.2eq), 2-chloroquine (16.3g, 0.1mol, 1.0eq), Cs2CO3(97.5g, 0.3mol, 3.0eq), and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged in a 3L round bottom flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Subsequently, the mixture was cooled to room temperature, and vacuum-concentrated using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of a saturated aqueous solution of sodium carbonate was slowly added, stirring was carried out, the layers were separated, the organic phase was washed successively with saturated sodium carbonate (300 ml. times.3), H2O (300 ml. times.3) and saturated sodium chloride (300 ml. times.3), sodium sulfate was dried and then filtered, the filtrate was vacuum-concentrated using a rotary evaporator to remove the organic solvent and obtain a crude product, and the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:2) as a mobile phase and vacuum-dried at 50 ℃ to obtain Compound 8(25.78g, yield: 83.4%).
As a result:
yield: 83.4 percent.
MS:m/z＝310.1(M+H+)；1HNMR(400M，d6-DMSO):8.05(dd，1H)，7.92(dd，1H)，7.62-7.73(m，3H)，7.42-7.51(m，5H)，7.14-7.25(m，2H)，2.35(s，3H).Anal.Calcd forC22H15NO:C，85.41；H，4.89；N，4.53.Found:C，85.41；H，4.89；N，4.53。
Synthesis of Compound 9
2- (4- (2-methyldibenzofuranyl)) quinoline (Compound 8) (9.27g, 0.03mol, 3.0eq) and iridium trichloride trihydrate (3.52g, 0.01mol, 1.0eq) were placed in a three-necked flask, 2-ethoxyethanol (66.7ml) and deionized water (33.3ml) were added, and the resulting mixture was reacted for 16hrs under a nitrogen blanket at about 110 ℃. Cooled to room temperature, filtered, and the filtrate was skimmed off, and the residue was dried with methanol (50 ml. times.3) and n-hexane (50 ml. times.3) in this order to give compound 9(5.15g, yield: 60.9%) as a gray solid. The obtained compound 9 was used in the next step without purification.
EXAMPLE 5 Synthesis of Compound CPD5
The dichloro bridge complex compound 9(4.23g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and acetylacetone (2.5g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the reaction was carried out at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 5. (2.06g, yield: 45.3%).
Results of CPD5 yield: 45.3 percent. MS M/z 909.2(M + H +).
Example 6 synthesis of compound CPD 6:
the dichloro bridge complex compound 9(4.23g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2, 8-dimethylnonane-4, 6-dione (4.6g, 25mmol, 10.0eq) were added in this order, and after the addition was complete, the reaction was carried out at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. Adding 1g of C salt and 200ml of dichloromethane into the reaction solution to dissolve the product, then filtering the mixed solution through a C salt bed, filtering the filtrate through a short silica gel column to obtain a filtrate, removing most of dichloromethane, adding 30ml of isopropanol into the filtrate to precipitate a red solid, and filtering. The solid is separated by column chromatography to obtain the target complex CPD 6. (1.98g, yield: 39.8%).
Results of CPD6 yield: 39.8 percent. MS M/z 993.3(M + H +).
EXAMPLE 7 Synthesis of Compound CPD7
The dichloro bridge complex compound 9(4.23g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2-acetylphenol (3.4g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the mixture was reacted at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 7. (1.51g, yield: 31.9%).
Results of CPD7 yield: 31.9 percent. MS M/z 945.2(M + H +).
EXAMPLE 8 Synthesis of Compound CPD8
The first step is as follows: synthesis of triflate
Dimer compound 9(33.78g, 0.02mol, 1.0eq) was dissolved in 1L of dichloromethane, to which was added silver trifluoromethanesulfonate (10.5g, 0.04mol, 2.0eq) and isopropanol (75ml) in that order. The mixture was stirred at room temperature overnight. The silver chloride was filtered off and the filtrate was spin dried to give 42g of product, which was used in the next reaction without purification.
The second step is that: synthesis of Compound CPD8
The product of the first step (21.56g, 0.02mol, 1.0eq) and 2-phenylpyridine (9.3g, 0.06mol, 3.0eq) were dissolved in 200ml of anhydrous ethanol, and the mixture was heated under reflux overnight under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, the precipitate was filtered and washed with methanol and n-hexane in sequence for 3 times. After drying at 50 ℃ in vacuo, the title compound CPD8(13.2g, yield 68.5%) was obtained. The dried CPD8 was used directly for sublimation purification to give the pure objective compound CPD8(10.8g, 81.82% yield) as a sublimated product.
EXAMPLE 9 Synthesis of Compound CPD9
Synthesis of Compound 10
Compound 7(27.12g, 0.12mol, 1.2eq), 2-chloro-5-isobutylquinaline (21.9g, 0.1mol, 1.0eq), Cs2CO3(97.5g, 0.3mol, 3.0eq) and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged into a 3L round-bottomed flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Subsequently, the mixture was cooled to room temperature, concentrated under vacuum using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of a saturated aqueous solution of sodium carbonate was slowly added, stirred, and the layers were separated, the organic phase was washed with saturated sodium carbonate (300 ml. times.3), H2O (300 ml. times.3), and saturated sodium chloride (300 ml. times.3) in this order, dried over sodium sulfate and filtered, the filtrate was concentrated under vacuum using a rotary evaporator to remove the organic solvent and obtain a crude product, and the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:3) as a mobile phase, and dried under vacuum at 50 ℃ to obtain Compound 10(25.78g, yield: 70.63%).
As a result:
yield: 70.63 percent.
MS:m/z＝366.2(M+H+)；1HNMR(400M，d6-DMSO):7.89(dd，1H)，7.82(dd，1H)，7.72(s，1H)，7.41-7.51(m，4H)，7.31(s，1H)，7.14-7.21(m，3H)，2.51(d，2H)，2.35(s，3H)，2.22(m，1H)，1.01(d，6H).Anal.Calcd for C26H23NO:C，85.45；H，6.34；N，3.83.Found:C，85.45；H，6.34；N，3.83。
Synthesis of compound 11:
2- (4- (2-methyldibenzofuranyl)) -5-isobutylquinoline (compound 10) (10.96g, 0.03mol, 3.0eq) and iridium trichloride trihydrate (3.52g, 0.01mol, 1.0eq) were placed in a three-necked flask, 2-ethoxyethanol (66.7ml) and deionized water (33.3ml) were added, and the resulting mixture was reacted for 16hrs at about 110 ℃ under nitrogen protection. Cooled to room temperature, filtered, and the filtrate was skimmed off, and the residue was dried with methanol (50 ml. times.3) and n-hexane (50 ml. times.3) in this order to give Compound 11 as a gray solid (5.64g, yield: 58.9%). The obtained compound 11 was used in the next step without purification.
Synthesis of compound CPD 9:
the dichloro bridge complex compound 11(4.78g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and acetylacetone (2.5g, 25mmol, 10.0eq) were added successively, and after completion of the addition, the reaction was carried out at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 9. (1.84g, yield: 36.01%).
Results of CPD9 yield: 36.01 percent. MS M/z 1021.4(M + H +).
EXAMPLE 10 Synthesis of Compound CPD13
Synthesis of compound 12:
compound 7(27.12g, 0.12mol, 1.2eq), 2-chloro-7-isobutylquinacrine (21.9g, 0.1mol, 1.0eq), Cs2CO3(97.5g, 0.3mol, 3.0eq) and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged into a 3L round-bottomed flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Subsequently, the mixture was cooled to room temperature, and vacuum-concentrated using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of a saturated aqueous solution of sodium carbonate was slowly added, stirring was carried out, the layers were separated, the organic phase was washed successively with saturated sodium carbonate (300 ml. times.3), H2O (300 ml. times.3) and saturated sodium chloride (300 ml. times.3), sodium sulfate was dried and then filtered, the filtrate was vacuum-concentrated using a rotary evaporator to remove the organic solvent and obtain a crude product, and the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:3) as a mobile phase and vacuum-dried at 50 ℃ to obtain Compound 13(24.26g, yield: 66.5%).
As a result:
yield: 66.5 percent.
MS:m/z＝366.2(M+H+)；1HNMR(400M，d6-DMSO):7.85(dd，1H)，，7.72-7.75(m，2H)，7.62(d，1H)，7.42-7.59(m，2H)，7.29-7.38(m，3H)，7.14-7.21(dd，2H)，2.51(d，2H)，2.35(s，3H)，2.22(m，1H)，1.01(d，6H).Anal.Calcd for C26H23NO:C，85.45；H，6.34；N，3.83.Found:C，85.45；H，6.34；N，3.83。
Synthesis of compound 13:
2- (4- (2-methyldibenzofuranyl)) -7-isobutylquinoline (compound 12) (10.96g, 0.03mol, 3.0eq) and iridium trichloride trihydrate (3.52g, 0.01mol, 1.0eq) were placed in a three-necked flask, 2-ethoxyethanol (66.7ml) and deionized water (33.3ml) were added, and the resulting mixture was reacted for 16hrs at about 110 ℃ under nitrogen protection. Cooled to room temperature, filtered, and the filtrate was skimmed off, and the residue was dried with methanol (50 ml. times.3) and n-hexane (50 ml. times.3) in this order to give compound 13(5.5g, yield: 57.4%) as a gray solid. The obtained compound 13 was used in the next step without purification.
Synthesis of compound CPD 13:
the dichloro bridge complex compound 13(4.78g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and acetylacetone (2.5g, 25mmol, 10.0eq) were added successively, and after the addition was completed, the reaction was carried out at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 13. (1.56g, yield: 30.53%).
Results of CPD13 yield: 30.53 percent. MS M/z 1021.4(M + H +).
Example 11 synthesis of compound CPD 18:
synthesis of compound 14:
compound 7(27.12g, 0.12mol, 1.2eq), 2-chloro-4-isobutyl-6-methyl-quinaline (23.3g, 0.1mol, 1.0eq), Cs2CO3(97.5g, 0.3mol, 3.0eq) and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged into a 3L round-bottomed flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Subsequently, the mixture was cooled to room temperature, and vacuum-concentrated using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of a saturated aqueous solution of sodium carbonate was slowly added, stirring was carried out, the layers were separated, the organic phase was washed successively with saturated sodium carbonate (300 ml. times.3), H2O (300 ml. times.3) and saturated sodium chloride (300 ml. times.3), sodium sulfate was dried and then filtered, the filtrate was vacuum-concentrated using a rotary evaporator to remove the organic solvent and obtain a crude product, and the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:3) as a mobile phase and vacuum-dried at 50 ℃ to obtain Compound 14(26.42g, yield: 69.5%).
As a result:
yield: 69.5 percent.
MS:m/z＝380.2(M+H+)；1HNMR(400M，d6-DMSO):7.95(d，1H)，7.72(s，1H)，7.41-7.51(m，4H)，7.31(s，1H)，7.14-7.21(m，3H)，2.51(d，2H)，2.35(s，3H)，2.31(s，3H)，2.22(m，1H)，1.01(d，6H).Anal.Calcd for C27H25NO:C，85.45；H，6.64；N，3.69.Found:C，85.45；H，6.64；N，3.69。
Synthesis of compound 15:
2- (4- (2-methyldibenzofuranyl)) -4-isobutyl-6-methylquinoline (compound 14) (11.38g, 0.03mol, 3.0eq) and iridium trichloride trihydrate (3.52g, 0.01mol, 1.0eq) were placed in a three-necked flask, 2-ethoxyethanol (66.7ml) and deionized water (33.3ml) were added, and the resulting mixture was reacted for 16hrs under a nitrogen blanket at about 110 ℃. Cooled to room temperature, filtered, and the filtrate was skimmed off, and the residue was dried with methanol (50 ml. times.3) and n-hexane (50 ml. times.3) in this order to give compound 15(5.18g, yield: 52.6%) as a gray solid. The obtained compound 15 was used in the next step without purification.
Synthesis of compound CPD 18:
dissolving the dichloro-bridge complex compound 15(4.93g, 2.5mmol, 1.0eq) in 2-ethoxyethanol (25ml), adding anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2, 8-dimethyl nonane-4, 6-dione (4.6g, 25mmol, 10.0eq) in sequence, reacting at 30 ℃ for 16hrs under the protection of nitrogen after the addition is finished, and cooling to room temperature. Adding 1g of C salt and 200ml of dichloromethane into the reaction solution to dissolve the product, then filtering the mixed solution through a C salt bed, filtering the filtrate through a short silica gel column to obtain a filtrate, removing most of dichloromethane, adding 30ml of isopropanol into the filtrate to precipitate a red solid, and filtering. The solid is separated by column chromatography to obtain the target complex CPD 18. (1.80g, yield: 34.31%).
Results of CPD18 yield: 34.31 percent. MS M/z 1133.5(M + H +).
EXAMPLE 12 Synthesis of Compound CPD22
Synthesis of compound 16:
compound 7(27.12g, 0.12mol, 1.2eq), 2-chloro-4-methyl-7-isobutylquinaline (23.3g, 0.1mol, 1.0eq), and Cs2CO3(97.5g, 0.3mol, 3.0eq) and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged into a 3L round-bottomed flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Subsequently, the mixture was cooled to room temperature, and vacuum-concentrated using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of a saturated aqueous solution of sodium carbonate was slowly added, stirring was carried out, the layers were separated, the organic phase was washed successively with saturated sodium carbonate (300 ml. times.3), H2O (300 ml. times.3) and saturated sodium chloride (300 ml. times.3), sodium sulfate was dried and then filtered, the filtrate was vacuum-concentrated using a rotary evaporator to remove the organic solvent and obtain a crude product, and the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:3) as a mobile phase and vacuum-dried at 50 ℃ to obtain Compound 16(27.00g, yield: 72.0%).
As a result:
yield: 72.0 percent.
MS:m/z＝380.2(M+H+)；1HNMR(400M，d6-DMSO):7.81(s，1H)，7.72(s，1H)，7.70(s，1H)，7.49(dd，1H)，7.42(dd，1H)，7.31(s，1H)，7.28(d，1H)，7.14-7.21(m，3H)，2.51(d，2H)，2.37(s，3H)，2.33(s，3H)，2.22(m，1H)，1.01(d，6H).Anal.Calcd for C27H25NO:C，85.45；H，6.64；N，3.69.Found:C，85.45；H，6.64；N，3.69。
Synthesis of compound 17:
2- (4- (2-methyldibenzofuranyl)) -4-methyl-7-isobutylquinoline (compound 16) (11.38g, 0.03mol, 3.0eq) and iridium trichloride trihydrate (3.52g, 0.01mol, 1.0eq) were placed in a three-necked flask, 2-ethoxyethanol (66.7ml) and deionized water (33.3ml) were added, and the resulting mixture was reacted for 16hrs under a nitrogen atmosphere at about 110 ℃. Cooled to room temperature, filtered, and the filtrate was skimmed off, and the residue was dried with methanol (50 ml. times.3) and n-hexane (50 ml. times.3) in this order to give Compound 17(4.82g, yield: 48.9%) as a gray solid. The obtained compound 17 was used in the next step without purification.
Synthesis of compound CPD 22:
the dichloro bridge complex compound 17(4.93g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2, 8-dimethylnonane-4, 6-dione (4.6g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the mixture was reacted at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. Adding 1g of C salt and 200ml of dichloromethane into the reaction solution to dissolve the product, then filtering the mixed solution through a C salt bed, filtering the filtrate through a short silica gel column to obtain a filtrate, removing most of dichloromethane, adding 30ml of isopropanol into the filtrate to precipitate a red solid, and filtering. The solid is separated by column chromatography to obtain the target complex CPD 22. (1.87g, yield: 33.01%).
Results of CPD22 yield: 33.01 percent. MS M/z 1133.5(M + H +).
Synthesis of common intermediate:
synthesis of compound 19:
compound 18(27.37g, 0.12mol, 1.2eq), 2-chloroquine (16.3g, 0.1mol, 1.0eq), Cs2CO3(97.5g, 0.3mol, 3.0eq), and Pd (dppf) Cl2(3.655g, 0.005mmol, 0.05eq) were charged in a 3L round bottom flask, 1L of anhydrous toluene was added, and stirring was refluxed at 110 ℃ for 16 hours under nitrogen. Subsequently, the mixture was cooled to room temperature, concentrated under vacuum using a rotary evaporator to remove the organic solvent, the residue was dissolved in 1L of dichloromethane, 500ml of a saturated aqueous solution of sodium carbonate was slowly added, stirred, and the layers were separated, the organic phase was washed with saturated sodium carbonate (300 ml. times.3), H2O (300 ml. times.3), and saturated sodium chloride (300 ml. times.3) in this order, dried over sodium sulfate and filtered, the filtrate was concentrated under vacuum using a rotary evaporator to remove the organic solvent and obtain a crude product, and the obtained crude product was purified by column chromatography using ethyl acetate/petroleum ether (volume ratio 1:2) as a mobile phase, and dried under vacuum at 50 ℃ to obtain Compound 19(26.7g, yield: 85.86%).
As a result:
yield: 85.86 percent.
MS:m/z＝312.1(M+H+)；1HNMR(400M，d6-DMSO):8.06(dd，1H)，8.03(dd，1H)，7.61-7.86(m，6H)，7.31-7.43(m，5H).Anal.Calcd for C21H13NS:C，81.00；H，4.21；N，4.50.Found:C，81.00；H，4.22；N，4.49。
Synthesis of compound 20:
2- (4-Dibenzothiophene) quinoline (Compound 19) (9.33g, 0.03mol, 3.0eq) and iridium trichloride trihydrate (3.52g, 0.01mol, 1.0eq) were placed in a three-necked flask, and 2-ethoxyethanol (66.7ml) and deionized water (33.3ml) were added to react the resulting mixture at about 110 ℃ for 16hrs under nitrogen protection. Cooled to room temperature, filtered, and the filtrate was skimmed off, and the residue was dried with methanol (50 ml. times.3) and n-hexane (50 ml. times.3) in this order to give compound 20(5.53g, yield: 65.2%) as a gray solid. The obtained compound 20 was used in the next step without purification.
EXAMPLE 13 Synthesis of Compound CPD25
The dichloro bridge complex compound 20(4.24g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and acetylacetone (2.5g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the reaction was carried out at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 25. (2.01g, yield: 43.9%).
Results of CPD25 yield: 43.9 percent. MS M/z 913.2(M + H +).
EXAMPLE 14 Synthesis of Compound CPD26
The dichloro bridge complex compound 20(4.24g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2, 8-dimethylnonane-4, 6-dione (4.6g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the mixture was reacted at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. Adding 1g of C salt and 200ml of dichloromethane into the reaction solution to dissolve the product, then filtering the mixed solution through a C salt bed, filtering the filtrate through a short silica gel column to obtain a filtrate, removing most of dichloromethane, adding 30ml of isopropanol into the filtrate to precipitate a red solid, and filtering. The solid is separated by column chromatography to obtain the target complex CPD 26. (1.98g, yield: 39.8%).
Results of CPD26 yield: 39.8 percent. MS M/z 997.3(M + H +).
EXAMPLE 15 Synthesis of Compound CPD27
The dichloro bridge complex compound 20(4.24g, 2.5mmol, 1.0eq) was dissolved in 2-ethoxyethanol (25ml), anhydrous sodium carbonate (6.9g, 50mmol, 20.0eq) and 2-acetylphenol (3.4g, 25mmol, 10.0eq) were added in this order, and after the addition was completed, the mixture was reacted at 30 ℃ for 16hrs under nitrogen protection, and then cooled to room temperature. 1g C salt and 200ml dichloromethane are added into the reaction solution to dissolve the product, then the mixed solution is filtered through a C salt bed, the filtrate is filtered through a short silica gel column, most dichloromethane is removed from the obtained filtrate, 30ml isopropanol is added into the filtrate, a red solid is separated out, and the red solid is filtered. The solid is separated by column chromatography to obtain the target complex CPD 27. (1.59g, yield: 33.5%).
Results of CPD27 yield: 33.5 percent. MS M/z 949.2(M + H +).
EXAMPLE 16 Synthesis of Compound CPD28
The first step is as follows: synthesis of triflate
Dimer compound 20(33.93g, 0.02mol, 1.0eq) was dissolved in 1L of dichloromethane, to which was added silver trifluoromethanesulfonate (10.5g, 0.04mol, 2.0eq) and isopropanol (75ml) in that order. The mixture was stirred at room temperature overnight. The silver chloride was filtered off and the filtrate was spin dried to give 42g of product, which was used in the next reaction without purification.
The second step is that: synthesis of Compound CPD28
The product of the first step (22.0g, 0.02mol, 1.0eq) and 2-phenylpyridine (9.3g, 0.06mol, 3.0eq) were dissolved in 200ml of anhydrous ethanol, and the mixture was heated under reflux overnight under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, the precipitate was filtered and washed with methanol and n-hexane in sequence for 3 times. After drying at 50 ℃ in vacuo, the title compound CPD28(13.42g, 69.4% yield) was obtained. The dried CPD28 was used directly for sublimation purification to afford CPD28(9.8g, 73.03% yield) as a pure sublimation target compound.
The corresponding compounds of other general formulas such as formula I, formula II, formula IV, formula V, formula VI and formula VII can be synthesized by the same similar method, and only the corresponding raw materials are selected.
Application example:
preparation of organic electroluminescent device
A glass substrate with an ITO transparent electrode having a thickness of 25 mm. times.75 mm. times.1.1 mm was ultrasonically washed in isopropyl alcohol for 5 minutes, and then subjected to ozone washing for 30 minutes. The thickness of the ITO film was set to 100 nm. The washed glass substrate with the transparent electrode line was mounted on a substrate holder of a vacuum deposition apparatus, and first, compound HATCN was deposited on the surface of the substrate on the side having the transparent electrode line so as to cover the transparent electrode, thereby forming a compound HATCN film having a thickness of 10nm, which film functions as a hole injection layer and also functions to planarize ITO. Then, HIL2 was vapor-deposited on the HATCN to form a film thickness of 125nm as a hole injecting material, and then, after completion of the evaporation of HIL2, HTM was vapor-deposited thereon to form a film thickness of 25nm as a hole transporting material. A light-emitting layer having a thickness of 25nm was formed by co-depositing Host and a dopant compound (corresponding to Cpd-X) on the HTM film, and the dopant material concentration was 10%. ETL as an electron transport material was deposited on the light-emitting layer to form an electron transport layer having a thickness of 20 nm. LiF is vapor-deposited on the electron transport layer to form a LiF layer having a film thickness of 1 nm. Metal Al was evaporated on LiF to form a metal cathode having a film thickness of 80 nm. The structure of the organic electroluminescent device is represented by a simple formula as follows: ITO (100nm)/HATCN (10nm)/HIL2(125nm)/HTM (25nm)/EML (Host: Dopantt ═ 90:10, 25nm)/ETL (20nm)/LiF (1nm)/Al (80 nm).
The devices fabricated as described above were subjected to performance testing, and the results are shown in table 1 below.
TABLE 1
Guest material Voltage/V Cd/A Lm/W CIEx CIEy LT90@1000nits
Cpd1 4.3 21 15.33 0.663 0.315 180
Cpd2 4.6 23 15.70 0.668 0.310 220
Cpd3 4.4 20 14.27 0.663 0.325 164
Cpd4 4.3 22 16.07 0.665 0.318 260
Cpd5 4.5 22 15.35 0.665 0.309 198
Cpd6 4.3 23 16.80 0.668 0.305 220
Cpd7 4.4 21 14.99 0.665 0.318 146
Cpd8 4.2 20 14.95 0.668 0.312 260
Cpd9 4.1 24 18.38 0.665 0.318 258
Cpd13 4.2 26 19.44 0.668 0.312 280
Cpd18 4.2 25 18.69 0.668 0.302 292
Cpd22 4.2 26 19.44 0.669 0.302 300
Cpd25 4.3 21 15.33 0.661 0.313 169
Cpd26 4.6 22 15.02 0.663 0.315 209
Cpd27 4.4 21 14.99 0.664 0.322 158
Cpd28 4.3 21 15.33 0.665 0.319 229
Comparative Cpd 5.3 14 8.29 0.660 0.330 108
As can be seen from the test results in table 1, the material of the present invention has not only higher luminous efficiency, but also more saturated red color scale, and the device lifetime is superior to that of the comparative example.
The results show that the metal complex designed by the invention is used as a guest material, and can convert triplet excitation energy into luminescence, so that the metal complex is applied to display devices such as organic electroluminescence and the like, the luminous efficiency of the devices can be improved, and the energy consumption can be reduced.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (15)

1. A compound using quinolyl dibenzo substitution as a ligand has a structure shown in formula I:
wherein,
z is selected from O, S, CR2, NR or Se, wherein R is alkyl, heteroalkyl, aryl or heteroaryl;
R1，R2，R3，R4are independently selected fromFrom hydrogen, alkyl, heteroalkyl, aryl or heteroaryl;
m is a metal;
X-Y is a monoanionic bidentate ligand;
the sum of a and b is the valence of the metal ion.
2. The compound of claim 1, wherein said compound has the following formula II:
3. a compound according to claim 1 or 2, wherein R is1，R2，R3Each independently is hydrogen, mono-, di-or poly-substituted, preferably mono-substituted.
4. A compound according to claim 1 or 2, wherein R is4Independently hydrogen or mono-or di-or polysubstituted, preferably hydrogen.
5. A compound according to claim 1 or 2, wherein R is1，R2Independently a substituent or a fused ring structure with the parent.
6. A compound according to claim 1 or 2, wherein R is1，R2，R3Independently an electron donating alkyl or heteroalkyl group of no more than four carbon atoms, preferably an electron donating branched alkyl group containing no more than 4 carbon atoms.
7. A compound according to claim 1 or 2, wherein R is3The substitution position of (b) is an adjacent position of a metal-carbon bond.
8. A compound according to claim 1 or 2, wherein R is3The substitution position of (b) is the relative position of the metal-carbon bond.
9. Compound according to claim 1 or 2, characterized in that M is a metal with an atomic coefficient greater than 40, preferably Cu, Pt, Pd, Os or Ir, more preferably Pt or Ir, especially Ir.
10. A compound according to claim 1 or 2, wherein X-Y is different from the left ligand.
11. A compound according to claim 1 or 2, characterized in that X-Y is a 1, 3-diketone.
12. The compound of claim 1 or 2, wherein the compound is of the structure:
13. the compound of claim 1 or 2, wherein the compound is of the structure:
14. an OLED phosphorescent guest material comprising a compound according to any one of claims 1 to 13.
15. An OLED device comprising a compound according to any one of claims 1 to 13.
CN201610918184.9A 2016-10-21 2016-10-21 The electroluminescent organic material of a kind of quinolyl dibenzo substitution as ligand and application thereof Pending CN107973823A (en)

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* Cited by examiner, † Cited by third party
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CN109593105A (en) * 2018-12-21 2019-04-09 北京诚志永华显示科技有限公司 Metal complex, organic electroluminescence device, electroluminescent organic material
WO2019093369A1 (en) * 2017-11-07 2019-05-16 三菱ケミカル株式会社 Iridium complex compound, composition containing said compound and solvent, organic electroluminescent element containing said compound, display device, and illumination device
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WO2020158689A1 (en) * 2019-01-30 2020-08-06 田中貴金属工業株式会社 Organic iridium complex for organic electroluminescent element
CN112341500A (en) * 2020-11-12 2021-02-09 马鞍山南大高新技术研究院有限公司 Iridium complex with main ligand containing carbazolyl and application
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DE102021112841A1 (en) 2020-05-19 2021-11-25 Beijing Summer Sprout Technology Co., Ltd. Organic, light-emitting material
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WO2022262309A1 (en) * 2021-06-18 2022-12-22 广东阿格蕾雅光电材料有限公司 Organometallic iridium compound and application thereof
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DE112021004918T5 (en) 2020-12-04 2023-07-13 Guangdong Aglaia Optoelectronic Materials Co., Ltd. METAL COMPLEX AND ITS APPLICATION
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1696137A (en) * 2005-04-30 2005-11-16 中国科学院长春应用化学研究所 Complexes of red light iridium by using nitrogen heterocycles in quinoline as ligand, and application
CN1802382A (en) * 2003-06-09 2006-07-12 日立化成工业株式会社 Metal coordination compound, polymer composition, and organic electroluminescence element using them
JP2013155153A (en) * 2012-01-31 2013-08-15 Osaka Prefecture Univ Carbazole derivative, host material for organic electroluminescent element, and organic electroluminescent element
CN104629741A (en) * 2013-11-14 2015-05-20 海洋王照明科技股份有限公司 Organic electrophosphorescence material, as well as preparation method and organic electroluminescent device thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1802382A (en) * 2003-06-09 2006-07-12 日立化成工业株式会社 Metal coordination compound, polymer composition, and organic electroluminescence element using them
CN1696137A (en) * 2005-04-30 2005-11-16 中国科学院长春应用化学研究所 Complexes of red light iridium by using nitrogen heterocycles in quinoline as ligand, and application
JP2013155153A (en) * 2012-01-31 2013-08-15 Osaka Prefecture Univ Carbazole derivative, host material for organic electroluminescent element, and organic electroluminescent element
CN104629741A (en) * 2013-11-14 2015-05-20 海洋王照明科技股份有限公司 Organic electrophosphorescence material, as well as preparation method and organic electroluminescent device thereof

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