CN104629741A - Organic electrophosphorescence material, as well as preparation method and organic electroluminescent device thereof - Google Patents

Organic electrophosphorescence material, as well as preparation method and organic electroluminescent device thereof Download PDF

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CN104629741A
CN104629741A CN201310571988.2A CN201310571988A CN104629741A CN 104629741 A CN104629741 A CN 104629741A CN 201310571988 A CN201310571988 A CN 201310571988A CN 104629741 A CN104629741 A CN 104629741A
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isoquinoline
compd
reaction
organic
preparation
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周明杰
王平
张娟娟
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention provides an organic electrophosphorescence material, as well as a preparation method and an organic electroluminescent device thereof. The organic electrophosphorescence material has a general formula (P), wherein R1 and R2 are straight chain or branched alkyl of C1-C8, and can be same or different. According to the organic electrophosphorescence material, 3-(substituted fluorene-2'-yl) isoquinoline serving as a cyclometalated ligand main structure and 2,2,6,6-tetramethyl-3,5-heptadione serving as an auxiliary ligand are used to synthesize a red-ray organic electrophosphorescence material iridium metallic disassortative complex, and the material luminescent colors can be adjusted by means of a chemical modifying method of introducing two alkyl groups on the 9-C bit of a fluorene ring in the cyclometalated ligand, so that the phosphorescence emission of different red luminescent wavelengths can be obtained.

Description

Organic electromechanical phosphorescent material and preparation method thereof and organic electroluminescence device
Technical field
The present invention relates to phosphor material field, particularly relate to a kind of organic electromechanical phosphorescent material.The invention still further relates to the preparation method of this organic electromechanical phosphorescent material and its application in organic electroluminescence device.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Make to stay cool to the research of organic electroluminescence device due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq 3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, obtained low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.
In order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Generally speaking, the development of blue phosphor materials always lags behind ruddiness and green glow, and with regard to single from this index of purity of color, blue phosphor materials seldom can accomplish the purity of color as dark red light and dark green light so far.In order to produce gratifying white light OLED, select at present or based on the phosphor material of sky blue light, as two [2-(4', 6'-difluorophenyl) pyridine-N, C 2'] (2-pyridine carboxylic acid) close iridium [FIrpic], it is just passable that this just requires that arranged in pairs or groups red phosphorescence material will be connected to saturated red scarlet.So the ruddiness phosphorescent organic electroluminescent material developing high color purity is still a large focus of OLED research field.
Summary of the invention
The object of the present invention is to provide a kind of new organic electromechanical phosphorescent material and preparation method thereof and organic electroluminescence device.For above-mentioned purpose, the invention provides the organic electromechanical phosphorescent material that one has following general formula (P):
Wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different.
The present invention also proposes a kind of preparation method of organic electromechanical phosphorescent material, and the method comprises the following steps:
A () provides following Compound C:
Described Compound C is wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different;
B () is under atmosphere of inert gases, by described Compound C and three hydrated iridium trichloride in molar ratio 2.2:1 ~ 3:1 be dissolved in reaction solvent, described reaction solvent is mixed by the cellosolvo of volume ratio 3:1 and water, reacting by heating system, make mixed solution stirring reaction 20 ~ 25h at 100 ~ 135 DEG C of temperature, after question response liquid is chilled to room temperature naturally, after product being washed drying, obtain compd B
C () provides following compd A:
Described compd A is 2,2,6,6-tetramethyl--3,5-heptadione, and structural formula is
D () is under atmosphere of inert gases, the described compd B obtained in described compd A, step (c) and alkaline catalysts are dissolved in reaction solvent, described compd A is 1.5 ~ 2 times of described three hydrated iridium trichloride molar weights, reacting by heating system, make mixed solution stirring reaction 5 ~ 7h at 100 ~ 120 DEG C of temperature, after question response liquid is chilled to room temperature naturally, separating-purifying reaction solution, obtains the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different.
In described step (b), the concentration range of described three hydrated iridium trichloride in described reaction solvent is 0.05 ~ 0.083mol/L; In described step (d), described reaction solvent is cellosolvo or 2-methyl cellosolve.
Described Compound C adopts following steps to obtain:
E () provides following Compound D;
Described Compound D is wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different;
F () is under atmosphere of inert gases, described Compound D, isoquinoline 99.9 and the alkaline catalysts aqueous solution are dissolved in reaction solvent, the mol ratio of described Compound D and 1-chlorine isoquinoline 99.9 is 1.1:1 ~ 1.2:1, palladium catalyst and phase-transfer catalyst is added after blasting argon purification, stirring reaction 2 ~ 5h at 100 ~ 120 DEG C of temperature, after being cooled to room temperature, separating-purifying, obtains described Compound C.
In described step (f), described isoquinoline 99.9 is 3-chlorine isoquinoline 99.9 or 1-chlorine isoquinoline 99.9, and described alkaline catalysts is salt of wormwood or sodium carbonate, and the consumption of described alkaline catalysts is 5.14 ~ 6.28 times of described isoquinoline 99.9 molar weight.
In described step (f), described reaction solvent is toluene or DMF, and the concentration range of described isoquinoline 99.9 in described reaction solvent is 0.064 ~ 0.08mol/L.
In described step (f), described palladium catalyst is tetra-triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium, and the consumption of described palladium catalyst is 4 ~ 6% of described isoquinoline 99.9 molar weight; Described phase-transfer catalyst is tri-n-octyl methyl ammonium chloride or Tetrabutyl amonium bromide, and the consumption of described phase-transfer catalyst is 10% of described isoquinoline 99.9 molar weight.
Described Compound D adopts following steps to obtain:
G () provides following compd E;
Described compd E is wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different;
H () is under atmosphere of inert gases, hexane solution containing n-Butyl Lithium is joined in the reaction flask that described compd E and reaction solvent are housed, the mol ratio of described compd E and n-Butyl Lithium is 1:1.2 ~ 1:1.5, the mixed solution obtained is stirred 30min at-78 DEG C of temperature, then Virahol tetramethyl ethylene ketone boric acid ester is added, question response system continues stirring reaction 2 ~ 4 hours after naturally rising to room temperature, add distilled water termination reaction, through extraction, filter, after separating-purifying, obtain described Compound D.
In described step (h), the mol ratio of described Virahol tetramethyl ethylene ketone boric acid ester and described n-Butyl Lithium is 1:1, and described reaction solvent is tetrahydrofuran (THF) or ether, and the concentration range of described compd E in described reaction solvent is 0.13 ~ 0.17mol/L.
The present invention also proposes a kind of organic electroluminescence device, it comprises anode layer, hole-injecting buffer layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and negative electrode, and the material of described luminescent layer is above-mentioned organic electromechanical phosphorescent material.
Compared with prior art, there is following advantage in organic electromechanical phosphorescent material of the present invention and preparation method thereof and organic electroluminescence device:
This organic electromechanical phosphorescent material is cyclic metal complexes agent structure with 3-(fluorenes-2'-base) isoquinoline 99.9, take methyl ethyl diketone as the different distribution type complex of iridium of assistant ligand.Isoquinoline 99.9 ring is the choosing of the superior structural of the ring master metal part of red phosphorescence material, can ensure that material is luminous at red spectral band; The 9-C position of fluorenes ring is introduced two identical or different alkyl groups, and the alkyl chain of different lengths is conducive to increasing material solvability in organic solvent on the one hand; The different electronic effect of alkyl group can realize the red emission of material different wave length on the other hand; In addition, two straight or branched type alkyl groups combine can produce very large space steric effect with the fluorenyls having large planar rigidity, this can reduce the direct effect between atoms metal, reduces the self-quenching phenomenon of triplet exciton, improves the luminous efficiency of material.The introducing of assistant ligand methyl ethyl diketone, effectively can improve the evaporation performance of material, increases its film-forming properties and improves the stability of device.
Accompanying drawing explanation
Fig. 1 is the photoluminescence spectrogram of electroluminescent organic material in embodiment 1;
Fig. 2 is the photoluminescence spectrogram of electroluminescent organic material in embodiment 2;
Fig. 3 is the photoluminescence spectrogram of electroluminescent organic material in embodiment 3;
Fig. 4 is the photoluminescence spectrogram of electroluminescent organic material in embodiment 4;
Fig. 5 is the structural representation of organic electroluminescence device in embodiment 5.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
The present invention has the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different; Namely the cyclic metal complexes of described organic electromechanical phosphorescent material can be following structure:
n=1～8
The synthetic route of organic electromechanical phosphorescent material of the present invention (P) is:
In sum, the synthetic route of organic electromechanical phosphorescent material provided by the invention (P) is specially:
Bromine fluorenes with two alkyl replacements first reacts with n-Butyl Lithium and reacts with Virahol tetramethyl ethylene ketone boric acid ester the tetramethyl ethylene ketone boric acid ester generating substituted fluorene again, then there is Suzuki linked reaction with 3-chlorine isoquinoline 99.9 and generate ring master metal part 3-(9 ', 9 '-dialkyl substituted fluorene-2 '-Ji) isoquinoline 99.9, then with IrCl 33H 2o reaction generates corresponding containing iridium chlorine bridge dipolymer, and last and assistant ligand source 2,2,6,6-tetramethyl--3,5-heptadione generation ligand exchange reaction obtains ultimate aim iridium metal complex.
With embodiment, organic electromechanical phosphorescent material of the present invention and preparation method thereof and organic electroluminescence device are specifically described below:
Embodiment 1
Organic electromechanical phosphorescent material disclosed in the present embodiment (P) is two [3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-tetramethyl ethylene ketone boric acid ester group-9,9-dimethyl fluorene
In argon atmosphere, be that the hexane solution of the n-Butyl Lithium (9mmol) of 1.6M joins 1.64g (6mmol) 2-bromo-9 is housed by 5.63ml concentration, in the 100ml bis-neck flask of 9-dimethyl fluorene and 40ml dry tetrahydrofuran (THF), mixed solution stirs 30min at-78 DEG C of temperature.Add 1.84ml (1.67g, 9mmol) Virahol tetramethyl ethylene ketone boric acid ester, question response system continues stirring reaction 2h after naturally rising to room temperature.Add 20ml distilled water termination reaction, by 50ml extracted with diethyl ether 3 times, merge organic phase.Organic phase uses anhydrous magnesium sulfate drying after saturated common salt water washing.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product with volume ratio be the ethyl acetate of 1:18 and the mixed solution of normal hexane for eluent is through silica gel column chromatography separating-purifying, after abundant drying 1.48g white solid be pure 2-tetramethyl ethylene ketone boric acid ester group-9,9-dimethyl fluorene, yield is 77.0%.
Structural Identification is carried out to above-mentioned product: mass spectrum (MS m/z): 320.2 (M +); Ultimate analysis: C 21h 25bO 2; Theoretical value: C, 78.76; H, 7.87; B, 3.38; O, 9.99; Measured value: C, 78.72; H, 7.93; B, 3.32; O, 10.03.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-tetramethyl ethylene ketone boric acid ester group-9,9-dimethyl fluorene.
(2) synthesis of 3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9
In argon atmosphere, salt of wormwood (20mmol) aqueous solution being 2.0M by 1.23g (3.85mmol) 2-tetramethyl ethylene ketone boric acid ester group-9,9-dimethyl fluorene, 0.57g (3.50mmol) 3-chlorine isoquinoline 99.9 and 10.0ml concentration is dissolved in 30ml toluene.0.16g (0.14mmol) tetrakis triphenylphosphine palladium and 0.16ml (0.35mmol) tri-n-octyl methyl ammonium chloride is added, stirring reaction 2h at 120 DEG C of temperature after blasting argon purification 20min in solution.Question response liquid uses appropriate extraction into ethyl acetate after being naturally chilled to room temperature.Anhydrous magnesium sulfate drying is used after the water washing of organic layer saturated common salt.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product is that the ethyl acetate/normal hexane mixed solution of 1:20 is separated through silica gel column chromatography for eluent with volume ratio, after abundant drying 0.86g white solid is pure 3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9, yield is 76.4%.
Structural Identification is carried out to above-mentioned product: mass spectrum (MS m/z): 321.4 (M +); Ultimate analysis: C 24h 19n; Theoretical value: C, 89.68; H, 5.96; N, 4.36; Measured value: C, 89.63; H, 6.02; N, 4.35.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9.
(3) title complex three [3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9-N, C 3'] close the synthesis of iridium
In the 30ml three-necked bottle being full of argon gas, it is in the cellosolvo/water mixed solvent of 3:1 that 0.71g (2.2mmol) 3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9 and 0.35g (1.0mmol) three hydrated iridium trichloride are dissolved in 12ml volume ratio.Reacting by heating system, makes mixed solution stirring reaction 24h at 120 DEG C of temperature.After question response liquid is chilled to room temperature naturally, collects the throw out in reaction solution, use methyl alcohol, n-hexane successively.After vacuum-drying ring master metal part be 3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer;
Then in the 50ml three-necked bottle being full of argon atmosphere, be 3-(9 ' by above-mentioned obtained ring master metal part, 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer, 0.31ml (1.5mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.32g (3.0mmol) Na 2cO 3be dissolved in 30ml2-ethoxy ethanol.Reacting by heating system, makes mixed solution stirring reaction 6h at 100 DEG C of temperature.After question response liquid is chilled to room temperature naturally, the throw out in collecting by filtration reaction solution, uses methyl alcohol, n-hexane successively.Filter residue is dissolved in q. s. methylene chloride, crosses and filters insolubles.Rotate the solvent steamed except in filtrate.Crude product take volume ratio as the methylene dichloride/normal hexane mixed solution of 1:22 is the separation of eluent silica gel column chromatography, obtain 0.27g solid with methylene dichloride/alcohol mixed solvent recrystallization again after abundant drying and be the two [3-(9 ' of pure title complex, 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium, yield is 26.6%.
Structural Identification: mass spectrum (MS m/z): 1016.4 (M +); Ultimate analysis: C 59h 55irN 2o 2; Theoretical value: C, 69.73; H, 5.45; Ir, 18.91; N, 2.76; O, 3.15; Measured value: C, 69.66; H, 5.52; Ir, 18.86; N, 2.83; O, 3.13.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two [3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
Figure 1 shows that title complex two [3-(9 ', 9 '-dimethyl fluorene-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium 2-methyltetrahydrofuran solution (~ 10 at 298K temperature -5mol/L) photoluminescence spectra in, transverse axis is emission wavelength (nm), and the longitudinal axis is the photoluminescence intensity after normalization method.As seen from the figure, the maximum emission peak of title complex photoluminescence spectra, at 617nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex 2-methyltetrahydrofuran solution of mol/L, with the fac-Ir (ppy) under the same terms 32-methyltetrahydrofuran solution be standard (phosphorescence quantum yield Φ p=0.40) Φ of title complex, is recorded p=0.08.
Embodiment 2
Organic electromechanical phosphorescent material disclosed in the present embodiment is title complex two [3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-n-hexyl fluorenes
In argon atmosphere, be that the hexane solution of the n-Butyl Lithium (7.5mmol) of 1.6M joins in the two neck flasks that the bromo-9-methyl of 2.06g (6mmol) 2--9-n-hexyl fluorenes and 35ml dry THF are housed by 4.69ml concentration, mixed solution stirs 30min at-78 DEG C of temperature.Add 1.53ml (1.40g, 7.5mmol) Virahol tetramethyl ethylene ketone boric acid ester, question response system continues stirring reaction 3h after naturally rising to room temperature.Add 20ml distilled water termination reaction, 40ml extracted with diethyl ether 3 times, merge organic phase.Organic phase uses anhydrous magnesium sulfate drying after saturated common salt water washing.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product with volume ratio be the ethyl acetate/normal hexane mixed solution of 1:12 for eluent is through silica gel column chromatography separating-purifying, after abundant drying 1.47g white solid be pure 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-n-hexyl fluorenes, yield is 62.8%.
Structural Identification is carried out to above-mentioned product: mass spectrum (MS m/z): 390.3 (M +); Ultimate analysis: C 26h 35bO 2; Theoretical value: C, 80.00; H, 9.04; B, 2.77; O, 8.20; Measured value: C, 80.04; H, 9.01; B, 2.73; O, 8.22.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-n-hexyl fluorenes.
(2) synthesis of 3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9
In argon atmosphere, salt of wormwood (22mmol) aqueous solution being 2.0M by 1.64g (4.20mmol) 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-n-hexyl fluorenes, 0.57g (3.50mmol) 3-chlorine isoquinoline 99.9 and 11.0ml concentration is dissolved in 40ml DMF (DMF).0.20g (0.175mmol) tetrakis triphenylphosphine palladium and 0.16ml (0.35mmol) tri-n-octyl methyl ammonium chloride is added, stirring reaction 5h at 100 DEG C of temperature after blasting argon purification 20min in solution.Question response liquid uses appropriate extraction into ethyl acetate after being naturally chilled to room temperature.Anhydrous magnesium sulfate drying is used after the water washing of organic layer saturated common salt.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product is that the ethyl acetate/normal hexane mixed solution of 1:18 is separated through silica gel column chromatography for eluent with volume ratio, after abundant drying 0.93g white solid is pure 3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9, yield is 67.9%.
Structural Identification is carried out to above-mentioned product: mass spectrum (MS m/z): 391.2 (M +); Ultimate analysis: C 29h 29n; Theoretical value: C, 88.96; H, 7.47; N, 3.58; Measured value: C, 88.93; H, 7.52; N, 3.55.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9.
(3) title complex three [3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] close the synthesis of iridium
In the 30ml three-necked bottle being full of argon atmosphere, it is in the cellosolvo/water mixed solvent of 3:1 that 0.98g (2.5mmol) 3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9 and 0.35g (1.0mmol) three hydrated iridium trichloride are dissolved in 15ml volume ratio.Reacting by heating system, makes mixed solution stirring reaction 20h at 135 DEG C of temperature.After question response liquid is chilled to room temperature naturally, collects the throw out in reaction solution, use methyl alcohol, n-hexane successively.After vacuum-drying ring master metal part be 3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer;
Then in the 50ml three-necked bottle being full of argon atmosphere, by above-mentioned obtained ring master metal part be 3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer 0.33ml (1.6mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.42g (4.0mmol) Na 2cO 3be dissolved in 20ml2-ethoxy ethanol.Reacting by heating system, makes mixed solution stirring reaction 5h at 120 DEG C of temperature.After question response liquid is chilled to room temperature naturally, the throw out in collecting by filtration reaction solution, uses methyl alcohol, n-hexane successively.Filter residue is dissolved in q. s. methylene chloride, crosses and filters insolubles.Rotate the solvent steamed except in filtrate.Crude product take volume ratio as the methylene dichloride/normal hexane mixed solution of 1:18 is the separation of eluent silica gel column chromatography, obtain 0.21g solid with methylene dichloride/alcohol mixed solvent recrystallization again after abundant drying and be pure title complex two [3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium, yield is 18.2%.
Structural Identification: mass spectrum (MS m/z): 1156.6 (M +); Ultimate analysis: C 69h 75irN 2o 2; Theoretical value: C, 71.66; H, 6.54; Ir, 16.62; N, 2.42; O, 2.77; Measured value: C, 71.63; H, 6.58; Ir, 16.55; N, 2.48; O, 2.76.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two [3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
Figure 2 shows that title complex two [3-(9 '-methyl-9 '-n-hexyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium 2-methyltetrahydrofuran solution (~ 10 at 298K temperature -5mol/L) photoluminescence spectra in, transverse axis is emission wavelength (nm), and the longitudinal axis is the photoluminescence intensity after normalization method.As seen from the figure, the maximum emission peak of title complex photoluminescence spectra, at 619nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex 2-methyltetrahydrofuran solution of mol/L, with the fac-Ir (ppy) under the same terms 32-methyltetrahydrofuran solution be standard (Φ p=0.40) Φ of title complex, is recorded p=0.09.
Embodiment 3
Organic electromechanical phosphorescent material disclosed in the present embodiment is title complex two [3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-tertiary butyl fluorenes
In argon atmosphere, be that the hexane solution of the n-Butyl Lithium (7.5mmol) of 1.6M joins in the two neck flasks that the bromo-9-methyl of 1.89g (6mmol) 2--9-tertiary butyl fluorenes and 35ml dry THF are housed by 4.69ml concentration, mixed solution stirs 30min at-78 DEG C of temperature.Add 1.53ml (1.40g, 7.5mmol) Virahol tetramethyl ethylene ketone boric acid ester, question response system continues stirring reaction 3h after naturally rising to room temperature.Add 20ml distilled water termination reaction, 40ml extracted with diethyl ether 3 times, merge organic phase.Organic phase uses anhydrous magnesium sulfate drying after saturated common salt water washing.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product with volume ratio be the ethyl acetate/normal hexane mixed solution of 1:15 for eluent is through silica gel column chromatography separating-purifying, after abundant drying 1.10g white solid be pure 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-tertiary butyl fluorenes, yield is 50.6%.
Structural Identification is carried out to above-mentioned product: mass spectrum (MS m/z): 362.2 (M +); Ultimate analysis: C 24h 31bO 2; Theoretical value: C, 79.56; H, 8.62; B, 2.98; O, 8.83; Measured value: C, 79.53; H, 8.67; B, 2.94; O, 8.86.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-tertiary butyl fluorenes.
(2) synthesis of 3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9
In argon atmosphere, salt of wormwood (22mmol) aqueous solution being 2.0M by 1.52g (4.20mmol) 2-tetramethyl ethylene ketone boric acid ester group-9-methyl-9-tertiary butyl fluorenes, 0.57g (3.50mmol) 1-chlorine isoquinoline 99.9 and 11.0ml concentration is dissolved in 40ml DMF (DMF).0.20g (0.175mmol) tetrakis triphenylphosphine palladium and 0.16ml (0.35mmol) tri-n-octyl methyl ammonium chloride is added, stirring reaction 5h at 100 DEG C of temperature after blasting argon purification 20min in solution.Question response liquid uses appropriate extraction into ethyl acetate after being naturally chilled to room temperature.Anhydrous magnesium sulfate drying is used after the water washing of organic layer saturated common salt.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product is that the ethyl acetate/normal hexane mixed solution of 1:16 is separated through silica gel column chromatography for eluent with volume ratio, after abundant drying 0.52g white solid is pure 3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9, yield is 40.9%.
Structural Identification is carried out to above-mentioned product: mass spectrum (MS m/z): 363.2 (M +); Ultimate analysis: C 27h 25n; Theoretical value: C, 89.21; H, 6.93; N, 3.85; Measured value: C, 89.25; H, 6.87; N, 3.88.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9.
(3) title complex three [3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] close the synthesis of iridium
In the 30ml three-necked bottle being full of argon atmosphere, it is in the cellosolvo/water mixed solvent of 3:1 that 0.91g (2.5mmol) 3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9 and 0.35g (1.0mmol) three hydrated iridium trichloride are dissolved in 15ml volume ratio.Reacting by heating system, makes mixed solution stirring reaction 24h at 120 DEG C of temperature.After question response liquid is chilled to room temperature naturally, collects the throw out in reaction solution, use methyl alcohol, n-hexane successively.After vacuum-drying ring master metal part be 3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer;
Then in the 50ml three-necked bottle being full of argon atmosphere, by above-mentioned obtained ring master metal part be 3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer, 0.33ml (1.6mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.42g (4.0mmol) Na 2cO 3be dissolved in 20ml2-ethoxy ethanol.Reacting by heating system, makes mixed solution stirring reaction 5h at 120 DEG C of temperature.After question response liquid is chilled to room temperature naturally, the throw out in collecting by filtration reaction solution, uses methyl alcohol, n-hexane successively.Filter residue is dissolved in q. s. methylene chloride, crosses and filters insolubles.Rotate the solvent steamed except in filtrate.Crude product take volume ratio as the methylene dichloride/normal hexane mixed solution of 1:20 is the separation of eluent silica gel column chromatography, obtain 0.22g solid with methylene dichloride/alcohol mixed solvent recrystallization again after abundant drying and be pure title complex two [3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium, yield is 20.0%.
Structural Identification: mass spectrum (MS m/z): 1100.5 (M +); Ultimate analysis: C 65h 67irN 2o 2; Theoretical value: C, 70.94; H, 6.14; Ir, 17.47; N, 2.55; O, 2.91; Measured value: C, 70.86; H, 6.23; Ir, 17.44; N, 2.57; O, 2.90.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two [3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
Figure 3 shows that title complex two [3-(9 '-methyl-9 '-tertiary butyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium 2-methyltetrahydrofuran solution (~ 10 at 298K temperature -5mol/L) photoluminescence spectra in, transverse axis is emission wavelength (nm), and the longitudinal axis is the photoluminescence intensity after normalization method.As seen from the figure, the maximum emission peak of title complex photoluminescence spectra, at 617nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex 2-methyltetrahydrofuran solution of mol/L, with the fac-Ir (ppy) under the same terms 32-methyltetrahydrofuran solution be standard (Φ p=0.40) Φ of title complex, is recorded p=0.13.
Embodiment 4
Organic electromechanical phosphorescent material disclosed in the present embodiment is title complex two [3-(9 ', 9 '-di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (methyl ethyl diketone) close iridium, its structural formula is as follows:
It adopts following steps to obtain:
(1) synthesis of 2-tetramethyl ethylene ketone boric acid ester group-9,9-di-n-octyl fluorenes
In argon atmosphere, be that the hexane solution of the n-Butyl Lithium (7.2mmol) of 1.6M joins 2.82g (6mmol) 2-bromo-9 is housed by 4.5ml concentration, in two neck flasks of 9 di-n-octyl fluorenes and 45ml dry ether, mixed solution stirs 30min at-78 DEG C of temperature.Add 1.47ml (1.34g, 7.2mmol) Virahol tetramethyl ethylene ketone boric acid ester, question response system continues stirring reaction 4h after naturally rising to room temperature.Add 20ml distilled water termination reaction, 40ml extracted with diethyl ether 3 times, merge organic phase.Organic phase uses anhydrous magnesium sulfate drying after saturated common salt water washing.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product with volume ratio be the ethyl acetate/normal hexane mixed solution of 1:10 for eluent is through silica gel column chromatography separating-purifying, after abundant drying 1.49g white solid be pure 2-tetramethyl ethylene ketone boric acid ester group-9,9-di-n-octyl fluorenes, yield is 48.1%.
Structural Identification: mass spectrum (MS m/z): 516.4 (M +); Ultimate analysis: C 35h 53bO 2; Theoretical value: C, 81.37; H, 10.34; B, 2.09; O, 6.19; Measured value: C, 81.33; H, 10.39; B, 2.05; O, 6.23.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-tetramethyl ethylene ketone boric acid ester group-9,9-di-n-octyl fluorenes.
(2) synthesis of 3-(9 ', 9 ' di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9
In argon atmosphere, sodium carbonate (18mmol) aqueous solution being 2.0M by 2.07g (4.00mmol) 2-tetramethyl ethylene ketone boric acid ester group-9,9-di-n-octyl fluorenes, 0.57g (3.50mmol) 3-chlorine isoquinoline 99.9 and 9.0ml concentration is dissolved in 35ml toluene.Two (triphenylphosphine) palladium of 0.15g (0.21mmol) dichloro and 0.11g (0.35mmol) Tetrabutyl amonium bromide is added, stirring reaction 4h at 110 DEG C of temperature after blasting argon purification 20min in solution.Question response liquid uses appropriate extraction into ethyl acetate after being naturally chilled to room temperature.Anhydrous magnesium sulfate drying is used after the water washing of organic layer saturated common salt.Filter, rotate the solvent steamed except in filtrate and obtain crude product.Crude product is that the ethyl acetate/normal hexane mixed solution of 1:15 is separated through silica gel column chromatography for eluent with volume ratio, after abundant drying 0.69g white solid is pure 3-(9 ', 9 ' di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9, yield is 38.1%.
Structural Identification is carried out to above-mentioned product: mass spectrum (MS m/z): 517.4 (M +); Ultimate analysis: C 38h 47n; Theoretical value: C, 88.15; H, 9.15; N, 2.71; Measured value: C, 88.18; H, 9.10; N, 2.72.The material that the above-mentioned reaction of above data acknowledgement obtains is 3-(9 ', 9 ' di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9.
(3) title complex three [3-(9 ', 9 ' di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] close the synthesis of iridium
In the 30ml three-necked bottle being full of argon atmosphere, it is in the cellosolvo/water mixed solvent of 3:1 that 1.55g (3mmol) 3-(9 ', 9 ' di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9 and 0.35g (1.0mmol) three hydrated iridium trichloride are dissolved in 20ml volume ratio.Reacting by heating system, makes mixed solution stirring reaction 25h at 100 DEG C of temperature.After question response liquid is chilled to room temperature naturally, collects the throw out in reaction solution, use methyl alcohol, n-hexane successively.After vacuum-drying ring master metal part be 3-(9 ', 9 ' di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer;
Then in the 50ml three-necked bottle being full of argon atmosphere, be 3-(9 ' by above-mentioned obtained ring master metal part, 9 ' di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9 containing iridium dichloro dimer, 0.42ml (2mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.48g (3.5mmol) K 2cO 3be dissolved in 30ml2-methyl cellosolve.Reacting by heating system, makes mixed solution stirring reaction 7h at 110 DEG C of temperature.After question response liquid is chilled to room temperature naturally, the throw out in collecting by filtration reaction solution, uses methyl alcohol, n-hexane successively.Filter residue is dissolved in q. s. methylene chloride, crosses and filters insolubles.Rotate the solvent steamed except in filtrate.Crude product take volume ratio as the methylene dichloride/normal hexane mixed solution of 1:15 is the separation of eluent silica gel column chromatography, obtain 0.18g solid with methylene dichloride/alcohol mixed solvent recrystallization again after abundant drying and be the two [3-(9 ' of pure title complex, 9 '-di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium, yield is 12.8%.
Structural Identification: mass spectrum (MS m/z): 1408.8 (M +); Ultimate analysis: C 87h 111irN 2o 2; Theoretical value: C, 74.16; H, 7.94; Ir, 13.64; N, 1.99; O, 2.27; Measured value: C, 74.11; H, 7.97; Ir, 13.66; N, 2.03; O, 2.23.The material that the above-mentioned reaction of above data acknowledgement obtains is title complex two [3-(9 ', 9 '-di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
Figure 4 shows that title complex two [3-(9 ', 9 '-di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium 2-methyltetrahydrofuran solution (~ 10 at 298K temperature -5mol/L) photoluminescence spectra in, transverse axis is emission wavelength (nm), and the longitudinal axis is the photoluminescence intensity after normalization method.As seen from the figure, the maximum emission peak of title complex photoluminescence spectra, at 621nm place, can be used as the preparation field that ruddiness electroluminescent material is widely used in organic electroluminescence device.
In addition, at 298K temperature, concentration is about 10 -5the title complex 2-methyltetrahydrofuran solution of mol/L, with the fac-Ir (ppy) under the same terms 32-methyltetrahydrofuran solution be standard (Φ p=0.40) Φ of title complex, is recorded p=0.10.
Embodiment 5
With the title complex that embodiment 4 is obtained two [3-(9 ', 9 '-di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium as luminescent layer doping object organic electroluminescence device, structure as shown in Figure 5:
This organic electroluminescence device is ITO (100nm)/NPB (65nm)/CBP:8wt%Ir title complex (30nm)/BCP (10nm)/Alq 3(20nm)/Liq (2nm)/Al (100nm).
The preparation technology of this organic electroluminescence device is as follows:
Through acetone, methyl alcohol, distilled water and the cleaned glass-based plate of Virahol adopt vacuum plating techniques of deposition a layer thickness to be 100nm, square resistance is that the tin indium oxide (ITO) of 20 Ω/mouth is as transparent anode 301, on anode 301, the NPB (N that a layer thickness is 65nm is prepared successively by vacuum evaporation, two (1-the naphthyl)-N of N'-, N '-diphenylbenzidine) material is as hole transmission layer 302, a layer thickness is the two [3-(9 ' prepared doped with 8wt% embodiment 4 of 30nm, 9 '-di-n-octyl fluorenes-2 '-Ji) isoquinoline 99.9-N, C 3'] (2,2,6,6-tetramethyl--3,5-heptadione) close the CBP (N of iridium, the two carbazyl-4 of N'-, 4'-dipyridyl) as luminescent layer 303, then vacuum evaporation a layer thickness is successively BCP (2, the 9-dimethyl-4 of 10nm on this luminescent layer 303,7-phenylbenzene-phenanthrolene) material is as hole blocking layer 304, and a layer thickness is the Alq of 20nm 3(three (oxine) aluminium) is that the Liq (oxine lithium) of 2nm is as electron injection buffer layer 306 as electron transfer layer 305, a layer thickness, last vacuum evaporation a layer thickness is on the buffer layer the metal A l of 100nm, as the negative electrode 307 of device.
Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, record the maximum emission wavelength of organic electroluminescence device at 622nm place, the maximum lumen efficiency of device is 7.11lm/W, and maximum current efficiency is 8.21cd/A.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.

Claims (10)

1. there is the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different.
2. a preparation method for organic electromechanical phosphorescent material, the method comprises the following steps:
A () provides following Compound C:
Described Compound C is wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different;
B () is under atmosphere of inert gases, by described Compound C and three hydrated iridium trichloride in molar ratio 2.2:1 ~ 3:1 be dissolved in reaction solvent, described reaction solvent is mixed by the cellosolvo of volume ratio 3:1 and water, reacting by heating system, make mixed solution stirring reaction 20 ~ 25h at 100 ~ 135 DEG C of temperature, after question response liquid is chilled to room temperature naturally, after product being washed drying, obtain compd B
C () provides following compd A:
Described compd A is 2,2,6,6-tetramethyl--3,5-heptadione, and structural formula is
D () is under atmosphere of inert gases, the described compd B obtained in described compd A, step (c) and alkaline catalysts are dissolved in reaction solvent, described compd A is 1.5 ~ 2 times of described three hydrated iridium trichloride molar weights, reacting by heating system, make mixed solution stirring reaction 5 ~ 7h at 100 ~ 120 DEG C of temperature, after question response liquid is chilled to room temperature naturally, separating-purifying reaction solution, obtains the organic electromechanical phosphorescent material of following general formula (P):
Wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different.
3. preparation method according to claim 2, is characterized in that, in described step (b), the concentration range of described three hydrated iridium trichloride in described reaction solvent is 0.05 ~ 0.083mol/L; In described step (d), described reaction solvent is cellosolvo or 2-methyl cellosolve, and the concentration of described compd A in described solvent is 0.05 ~ 0.08mol/L; Described alkaline catalysts is salt of wormwood or sodium carbonate, and consumption is 1.75 ~ 2.5 times of described compd A molar weight.
4. preparation method according to claim 3, is characterized in that, described Compound C adopts following steps to obtain:
E () provides following Compound D;
Described Compound D is wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different;
F () is under atmosphere of inert gases, described Compound D, isoquinoline 99.9 and the alkaline catalysts aqueous solution are dissolved in reaction solvent, the mol ratio of described Compound D and 1-chlorine isoquinoline 99.9 is 1.1:1 ~ 1.2:1, palladium catalyst and phase-transfer catalyst is added after blasting argon purification, stirring reaction 2 ~ 5h at 100 ~ 120 DEG C of temperature, after being cooled to room temperature, separating-purifying, obtains described Compound C.
5. preparation method according to claim 4, it is characterized in that, in described step (f), described isoquinoline 99.9 is 3-chlorine isoquinoline 99.9 or 1-chlorine isoquinoline 99.9, described alkaline catalysts is salt of wormwood or sodium carbonate, and the consumption of described alkaline catalysts is 5.14 ~ 6.28 times of described isoquinoline 99.9 molar weight.
6. preparation method according to claim 4, is characterized in that, in described step (f), described reaction solvent is toluene or DMF, and the concentration range of described isoquinoline 99.9 in described reaction solvent is 0.064 ~ 0.08mol/L.
7. preparation method according to claim 4, is characterized in that, in described step (f), described palladium catalyst is tetra-triphenylphosphine palladium or dichloro bi triphenyl phosphine palladium, and the consumption of described palladium catalyst is 4 ~ 6% of described isoquinoline 99.9 molar weight; Described phase-transfer catalyst is tri-n-octyl methyl ammonium chloride or Tetrabutyl amonium bromide, and the consumption of described phase-transfer catalyst is 10% of described isoquinoline 99.9 molar weight.
8. preparation method according to claim 7, is characterized in that, described Compound D adopts following steps to obtain:
G () provides following compd E;
Described compd E is wherein, R 1, R 2for C 1 ~ 8straight or branched alkyl, R 1, R 2identical or different;
H () is under atmosphere of inert gases, hexane solution containing n-Butyl Lithium is joined in the reaction flask that described compd E and reaction solvent are housed, the mol ratio of described compd E and n-Butyl Lithium is 1:1.2 ~ 1:1.5, the mixed solution obtained is stirred 30min at-78 DEG C of temperature, then Virahol tetramethyl ethylene ketone boric acid ester is added, question response system continues stirring reaction 2 ~ 4 hours after naturally rising to room temperature, add distilled water termination reaction, through extraction, filter, after separating-purifying, obtain described Compound D.
9. preparation method according to claim 8, it is characterized in that, in described step (h), the mol ratio of described Virahol tetramethyl ethylene ketone boric acid ester and described n-Butyl Lithium is 1:1, described reaction solvent is tetrahydrofuran (THF) or ether, and the concentration range of described compd E in described reaction solvent is 0.13 ~ 0.17mol/L.
10. an organic electroluminescence device, comprise anode layer, hole-injecting buffer layer, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and negative electrode, it is characterized in that, the material of described luminescent layer is organic electromechanical phosphorescent material according to claim 1.
CN201310571988.2A 2013-11-14 2013-11-14 Organic electrophosphorescence material, as well as preparation method and organic electroluminescent device thereof Pending CN104629741A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107163082A (en) * 2016-03-08 2017-09-15 上海和辉光电有限公司 A kind of organic compound and OLED display
CN107973823A (en) * 2016-10-21 2018-05-01 上海和辉光电有限公司 The electroluminescent organic material of a kind of quinolyl dibenzo substitution as ligand and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107163082A (en) * 2016-03-08 2017-09-15 上海和辉光电有限公司 A kind of organic compound and OLED display
CN107973823A (en) * 2016-10-21 2018-05-01 上海和辉光电有限公司 The electroluminescent organic material of a kind of quinolyl dibenzo substitution as ligand and application thereof

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