CN109206458A - Red phosphorescent compound and the organic light emitting diode device for using the compound - Google Patents
Red phosphorescent compound and the organic light emitting diode device for using the compound Download PDFInfo
- Publication number
- CN109206458A CN109206458A CN201811026991.5A CN201811026991A CN109206458A CN 109206458 A CN109206458 A CN 109206458A CN 201811026991 A CN201811026991 A CN 201811026991A CN 109206458 A CN109206458 A CN 109206458A
- Authority
- CN
- China
- Prior art keywords
- red phosphorescent
- phosphorescent compound
- layer
- grams
- light emitting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Abstract
The invention discloses a kind of red phosphorescent compound and use the organic light emitting diode device of the red phosphorescent compound.A kind of red phosphorescent compound provided by the invention, shown in structural formula as I,Wherein,It indicatesWherein, R1, R2, R3 and R4 are independently selected from H, C1~C6 alkyl one kind.In formula (I)It indicates to be selected from specific alkane diketone and its derivative.Device described in organic electroluminescence device provided by the invention includes the anode being sequentially deposited each other, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode；The organic electroluminescence device includes above-mentioned red phosphorescent compound as dopant.Red phosphorescent compound provided by the invention can make organic light emitting diode device have high efficiency and high color purity and narrow spectrum.
Description
Technical field
The present invention relates to a kind of organic electroluminescent diode components, in particular to red phosphorescent compound and use
Its organic light emitting diode device.Particularly, the present invention relates to the doping for the luminescent layer for being used as organic light emitting diode device
The red-emitting phosphor of agent.
Background technique
In recent years, as the size of display device is increasing, the flat-panel monitor for occupying less space is had increasing need for
Part.The flat-panel display device includes organic electroluminescence device, also referred to as Organic Light Emitting Diode (OLED).The organic light emission two
With the development of huge speed, many prototypes have been disclosed in the technology of pole pipe device.
When charge is injected into the organic layer formed between electron injection electrode (cathode) and hole injecting electrode (anode)
When, organic electroluminescence device shines.More specifically, shine when electrons and holes form a clock synchronization, newly generated electron hole
To decaying.Organic electroluminescence device can be formed in flexible transparent substrate such as plastics.It can also be shown than plasma
It is driven under the lower voltage of required voltage (voltage for being less than or equal to 10V) in plate or inorganic EL (EL) display
Organic electroluminescence device.Organic electroluminescence device is advantageous in that, is consumed compared with other display devices less
Energy and excellent color be provided show.Moreover, because organic electroluminescence device using three colors (it is i.e. green, it is blue and red
Color), it can be with reproduced picture, so organic electroluminescence device is broadly considered the next-generation face that can reproduce clear image
Color display device.
The process description for manufacturing Organic Light Emitting Diode (EL) device is as follows:
(1) on the transparent substrate by anode material coating.Generally make anode material using tin indium oxide (ITO).
(2) deposition of hole implanted layer (HIL) on anode material.Hole injection layer is by with 10 nanometers (nm) to 30 (nm)
Copper phthalocyanine (CuPc) layer of thickness is formed.
(3) hollow transport layer (HTL) is then deposited.Hole transmission layer is mainly by 4,4 '-bis- [N- (1- naphthalene)-N- phenylaminos
Base] biphenyl (NPB) formation, it is first handled with vacuum evaporation, is then applied to the thickness with 30 nanometers (nm) to 60 nanometers (nm).
(4) hereafter, organic luminous layer is formed.At this time, if it is desired, dopant can be added.In the case where green light,
Organic luminous layer is generally by being evaporated in vacuo to three (8-hydroxyquinoline acid) aluminium with 30 nanometers (nm) to 60 nanometers (nm) thickness
(Alq3) it is formed.And it uses, MQD (N- methyl quinacridine copper) is used as dopant (or impurity).
(5) electron transfer layer (ETL) and electron injecting layer (EIL) are sequentially formed on organic luminous layer, or in organic hair
Electron injection/transport layer is formed on photosphere.In the case where green light, the Alq3 of step (4) has excellent electron-transport energy
Power.Therefore, it is not necessary to which ground needs electron injection and transport layer.
(6) last coated cathode layer, over the entire structure coat protective layer.
According to the method for forming luminescent layer in said structure, determines and issue (or display) indigo plant respectively, it is green, red color
Luminescent device.As luminescent material, exciton is formed by the recombination of the electrons and holes from each electrode injection.Singlet exciton
Emit fluorescence, triplet excitons emit phosphorescence.The singlet exciton for emitting fluorescence has 25% formation possibility, and emits phosphorus
The triplet excitons of light have 75% formation possibility.
Therefore, compared with singlet exciton, triplet excitons provide bigger luminous efficiency.In such phosphor material
In, red phosphorescence material can have bigger luminous efficiency than fluorescent material.Therefore, as raising organic electroluminescence device
Efficiency an important factor for, red phosphorescence material is being widely studied.
When using such phosphorescene materials, high-luminous-efficiency, high color purity and extended durability are needed.Most especially
Ground increases (i.e. the X value of cie color coordinate becomes much larger) with excitation purity when using red phosphorescence material, it is seen that and degree reduces,
So as to cause being difficult to provide high-luminous-efficiency.Therefore, it is necessary to develop can provide excellent chromaticity coordinate (the CIE excitation purity of X=
0.63 or more), the red phosphorescence material of the luminous efficiency of raising and extended durability.
Summary of the invention
This invention address that providing red phosphorescent compound and the Organic Light Emitting Diode using the red phosphorescent compound
Device, which substantially obviate the limitation and disadvantage due to the relevant technologies caused by one or more problems.
It is an advantage of the invention to provide a kind of compounds as making in the luminescent layer of organic light emitting diode device
For dopant, to provide the organic electroluminescence with high color purity, high brightness and long wearing, structural formula as I institute
Show,
Wherein,It indicates
Wherein, R1, R2, R3 and R4 are independently selected from H, C1~C6 alkyl one kind.
And wherein,Indicate alkane diketone and its derivative chosen from the followings:
Preferably, C1~C6 alkyl is selected from methyl, methyl-d3, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl
One of base and tert-butyl.
Specifically, Formulas I can be any of following chemical formula:
It is another object of the present invention to provide a kind of organic light emitting diode devices, including the sun being sequentially deposited each other
The organic electroluminescence of pole, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode
Part, the organic light emitting diode device include above-mentioned any red phosphorescent compound as dopant.
Preferably, appointing in Al and Zn metal complex and carbazole derivates is used in the organic light emitting diode device
The amount ranges of a kind of material of main part as luminescent layer, dopant can be within the scope of 0.1 weight of weight %~50 %.When making
The amount of dopant within the above range when, efficiency of the invention can be improved.
Preferably, the ligand of the Al or Zn metal complex is quinolyl, xenyl, isoquinolyl, phenyl, methyl quinoline
One or more of quinoline base, dimethyl quinoline base, dimethyl-isoquinolyl；The carbazole derivates are 4,4 '-N, the N click of '-two
Biphenyl (CBP).
Red phosphorescent compound provided by the invention can make organic light emitting diode device have high efficiency and high color purity
With narrow spectrum.
Detailed description of the invention
Fig. 1 is the figure of the relationship of wavelength and relative sensitivity.
Specific embodiment
The example of preferred embodiment described below is to describe the present invention.It will be apparent that the present invention not only office
It is limited to proposed embodiment.
Due to the red phosphorescent compound of structural formula as I be provide excellent chromaticity coordinate (the CIE excitation purity of X=
0.67 or more), the red phosphorescence material of the luminous efficiency of raising and extended durability, now with RD-001, RD-361, RD-
002, for RD-362, RD-006 and RD-366 preparation method and test result, it was demonstrated that technical solution provided by the invention and reach
The technical effect arrived.
Fig. 1 illustrates to indicate to increase (becoming much larger with the X value of chromaticity coordinate) with the excitation purity of organic electroluminescence device
The figure that visibility reduces.
In following embodiments, NPB 4,4 '-bis- [N- (1- naphthalene)-N- phenylamino] biphenyl, CBP 4,4 '-N, N '-
Two click biphenyl, CuPc are CuPc, and LiF lithium fluoride, ITO is tin indium oxide, and Alq3 is three (8-hydroxyquinoline) aluminium.
LC-MS: liquid chromatograph-mass spectrometer, M/Z: proton number/charge number ratio.
The following figure is compound copper (II) phthalocyanine (CuPc) used in embodiments of the invention, NPB, (btp) 2Ir
(acac), the structural formula of Alq3 and CBP.
The synthesis of 1.5- (2- methyl-propyl) quinoline
By 80 grams of 5- bromoquinoline (0.38mmol), 78.4 grams of isobutaneboronic acid (0.77mol), three (dibenzalacetones) two
Palladium (2mol%), 2- dicyclohexyl phosphine -2', 6'- dimethoxy-biphenyl (4mol%), 354 grams of potassium phosphate (single water)
(1.54mol), 800mL toluene, nitrogen displacement, and heating reflux reaction is left 18 hours in nitrogen protection state.By reactant
System is down to room temperature, is that column purification is crossed in n-hexane/ethyl acetate=100/2 with eluent, obtains 52.8 grams of (yields: 75%) 5-
(2- methyl-propyl) quinoline.
LC-MS:M/Z 186.3 (M+H)+
The synthesis of 2.1- oxidation -5- isobutyl quinoline
By 5- 52 grams of quinoline of (2- methyl-propyl) (0.28mol) in three-necked bottle, it is dissolved in acetic acid 500ml, is slowly added to double
Oxygen water 200mL.Slow temperature reaction system is stirred at reflux to 80 DEG C.Stop reaction after back flow reaction 12h.Acetic acid is distilled off,
Reaction mixture is extracted with ethyl acetate and water, takes organic phase anhydrous magnesium sulfate dry.Organic phase after drying is evaporated, thick to produce
Object recrystallizes separating-purifying by tetrahydrofuran and methanol solvate and obtains 32.8 grams of final product (yield: 58%) 1- oxidation -5-
Isobutyl quinoline.
LC-MS:M/Z 202.3 (M+H)+
The synthesis of 3.2- chlorination -5- isobutyl quinoline
32 grams of 1- oxidation -5- isobutyl quinoline (0.16mol) is added in three-necked bottle, 31.7 grams of phosphorus oxychloride
(0.21mol) and methylene chloride 400mL.Temperature reaction system to 50 DEG C flow back.Stop reaction after back flow reaction 6h.It is distilled off
Acetic acid extracts reaction mixture with ethyl acetate and water, takes organic phase anhydrous magnesium sulfate dry.Organic phase after drying is dense
Contracting, crude product obtain 24.5 grams of product by chromatographic silica gel post separating-purifying with the mixed solvent of ethyl acetate and n-hexane 1:40
(yield: 70%) 2- chlorination -5- isobutyl group quinoline.LC-MS:M/Z 220.7 (M+H)+
4. the synthesis of cyclohexene -1- pinacol borate
Under the conditions of nitrogen protection, into there-necked flask be added bromo- 20 grams of 1- cyclohexene (0.12mol) of 1-, connection boric acid frequency that
34.7 grams of alcohol ester (0.14mol), 2.0 grams of triphenylphosphine (6mol%), trans- two 2.6 grams of (triphenylphosphine) palladium chloride (II)
(3mol%), 24.6 grams of potassium phenate (0.19mol) and dry toluene 250mL.5 are stirred to react under the conditions of 50 DEG C after nitrogen displacement
Hour, system is then cooled to room temperature and adds water quenching reaction.Reaction mixture benzene solvent and saturated salt solution extraction.It takes
Organic phase is dry with anhydrous magnesium sulfate.Mixture after drying is filtered and is concentrated under reduced pressure, silica gel column chromatography or distillation can be passed through
Method is purified to obtain 21.9 grams of (yields: 85%) cyclohexene -1- pinacol borate.LC-MS:M/Z 209.1 (M+H)+
The synthesis of 5.3- methylcyclohexene -1- pinacol borate
Under the conditions of nitrogen protection, the bromo- 3- methyl-1 of 1- -15 grams of cyclohexene (85.7mmol), connection are added into there-necked flask
23.9 grams of boric acid pinacol ester (94.2mmol), 1.4 grams of triphenylphosphine (6mol%), trans- two (triphenylphosphine) palladium chloride
(II) 1.8 grams (3mol%), 20.0 grams of potassium phenate (128.5mol) and dry toluene 200mL.In 50 DEG C of conditions after nitrogen displacement
Under be stirred to react 5 hours, system is then cooled to room temperature and adds water quenching reaction.Reaction mixture benzene solvent and saturation food
Salt water extraction.Take organic phase anhydrous magnesium sulfate dry.Mixture after drying is filtered and is concentrated under reduced pressure, silica gel column chromatography can be passed through
Column or the way of distillation are purified to obtain 15.6 grams of (yields: 82%) 3- methylcyclohexene -1- pinacol borate.LC-MS:M/
Z 223.1(M+H)+
The synthesis of 6.3,5- dimethylcyclohexenes -1- pinacol borate
Under the conditions of nitrogen protection, bromo- 15 grams of 3,5- dimethyl -1- cyclohexene of 1- are added into there-necked flask
(79.3mmol), 34.7 grams of connection boric acid pinacol ester (87.26mmol), 1.3 grams of triphenylphosphine (6mol%), trans- two (triphenyl
Phosphine) 1.7 grams of palladium chloride (II) (3mol%), 15.7 grams of potassium phenate (119mmol) and dry toluene 200mL.After nitrogen displacement
It is stirred to react under the conditions of 50 DEG C 5 hours, system is then cooled to room temperature and adds water quenching reaction.Reaction mixture benzene is molten
Agent and saturated salt solution extraction.Take organic phase anhydrous magnesium sulfate dry.Mixture after drying is filtered and is concentrated under reduced pressure, can be led to
It crosses silica gel column chromatography or the way of distillation is purified to obtain 14.1 grams of (yields: 75%) 3,5- dimethylcyclohexenes -1- boric acid frequency
Any alcohol ester.LC-MS:M/Z 237.2 (M+H)+
The synthesis of 7.2- (hexamethylene -1- alkene -1- base) -5- isobutyl group quinoline
Under nitrogen protection, 6 grams of 2- chlorination -5- isobutyl quinoline (27.3mmol) is added into there-necked flask, cyclohexene -1-
6.3 grams of pinacol borate (30mmol), 2M- potassium carbonate 60mL is dissolved in nitrogen in tetrahydrofuran 60mL and replaces 30 minutes, is added
Catalyst tetra-triphenylphosphine palladium (1mol%).Reaction system is warming up to 80 DEG C, is stirred at reflux 12 hours.It is cooled to room temperature, adds
Water quenching reaction, extracts reaction solution with ethyl acetate and saturated salt solution.With saturated common salt water washing two to three times, take organic
Phase.It is concentrated after organic phase anhydrous magnesium sulfate drying.5.7 grams of (yields: 78%) 2- can be obtained by silica gel column chromatography separating-purifying
(hexamethylene -1- alkene -1- base) -5- isobutyl group quinoline.LC-MS:M/Z 266.4 (M+H)+
The synthesis of 8.5- isobutyl group -2- (3- methyl cyclohexane -1- alkene -1- base) quinoline
Under nitrogen protection, 6 grams of 2- chlorination -5- isobutyl quinoline (27.3mmol) is added into there-necked flask, 3- methyl ring
6.7 grams of hexene -1- pinacol borate (30mmol), 2M- potassium carbonate 60mL are dissolved in nitrogen in tetrahydrofuran 60mL and replace 30 points
Clock is added catalyst tetra-triphenylphosphine palladium (1mol%).Reaction system is warming up to 80 DEG C, is stirred at reflux 12 hours.It is cooled to
Room temperature adds water quenching reaction, extracts reaction solution with ethyl acetate and saturated salt solution.It is arrived three times with saturated common salt water washing two,
Take organic phase.It is concentrated after organic phase anhydrous magnesium sulfate drying.By silica gel column chromatography separating-purifying can obtain 5.7 grams (yield:
76%) 5- isobutyl group -2- (3- methyl cyclohexane -1- alkene -1- base) quinoline.LC-MS:M/Z 280.4 (M+H)+
The synthesis of 9.5- isobutyl group -2- (3,5- dimethyleyelohexane -1- alkene -1- base) quinoline
By 3 grams of monohydrate (10mmol) of iridous chloride, 2- (hexamethylene -1- alkene -1- base) 5.9 grams of -5- isobutyl group quinoline
The ratio of (22.1mmol) and diethanol list ether and distilled water is the mixed solution of 3/1 (120mL/40mL), is added dry
In two mouthfuls of round-bottomed flasks, heating reflux reaction 24 hours, suitable distilled water is then added, then the solid of precipitation is filtered, and
With methanol and petroleum ether solid, 4.9 grams of (yields: 65%) dichloro crosslinking Dimer Complex are obtained.LC-MS:M/Z
1513.9(M+H)+
10. the synthesis of dichloro crosslinking Dimer Complex
By 3 grams of monohydrate (10mmol) of iridous chloride, 2- (hexamethylene -1- alkene -1- base) 5.9 grams of -5- isobutyl group quinoline
The ratio of (22.1mmol) and diethanol list ether and distilled water is the mixed solution of 3/1 (120mL/40mL), is added dry
In two mouthfuls of round-bottomed flasks, heating reflux reaction 24 hours, suitable distilled water is then added, then the solid of precipitation is filtered, and
With methanol and petroleum ether solid, 4.9 grams of (yields: 65%) dichloro crosslinking Dimer Complex are obtained.LC-MS:M/Z
1513.9(M+H)+
The synthesis of 11.RD-001
By dichloro be crosslinked 3 grams of Dimer Complex (1.98mmol), 1 gram of pentane -2,4- diketone (9.9mmol), anhydrous carbon
Sour sodium 1.3 grams (11.9mmol) and cellosolvo 80ml are added in twoport round-bottomed flask, and then heating reflux reaction 6 is small
When, stop heating, is down to room temperature, suitable distilled water is added, filters out solid.In methylene chloride by solid dissolution, silicon is crossed
Glue short column.Solvent is removed at reduced pressure conditions, and the solid being concentrated to get successively uses methanol and petroleum ether, obtains 2.2 grams and (receives
Rate: 68%) required product.LC-MS:M/Z 821.1(M+H)+
The synthesis of 12.RD-361
Dichloro is crosslinked 3 grams of Dimer Complex (1.98mmol), 3,7- 1.3 grams of diketone of diethyl -5- methyl -4,6- nonyls
(5.9mmol), in 1.3 grams of natrium carbonicum calcinatum (11.9mmol) and cellosolvo 80ml addition twoport round-bottomed flasks, then
Heating reflux reaction 6 hours, stops heating, be down to room temperature, suitable distilled water is added, filters out solid.Solid is dissolved in
In methylene chloride, short column of silica gel is crossed.Solvent is removed at reduced pressure conditions, and the solid being concentrated to get successively is washed with methanol and petroleum ether
It washs, obtains 2.5 grams of (yields: 68%) required product.LC-MS:M/Z 933.3(M+H)+
13. the synthesis that dichloro is crosslinked the synthesis of Dimer Complex
By 3 grams of monohydrate (10mmol) of iridous chloride, 5- isobutyl group -2- (3- methyl cyclohexane -1- alkene -1- base) quinoline
The ratio of 6.2 grams (22.1mmol) and diethanol list ether and distilled water is the mixed solution of 3/1 (120mL/40mL), is added dry
In two mouthfuls of dry round-bottomed flasks, heating reflux reaction 24 hours, it is then added suitable distilled water, then by the solid mistake of precipitation
Filter, and use methanol and petroleum ether solid, obtain 4.7 grams (yields: 60%) dichloro be crosslinked Dimer Complex.LC-MS:M/
Z 1570(M+H)+
The synthesis of 14.RD-002
By dichloro be crosslinked 3 grams of Dimer Complex (1.9mmol), 1 gram of pentane -2,4- diketone (9.6mmol), Carbon Dioxide
In 1.2 grams of sodium (11.5mmol) and cellosolvo 80ml addition twoport round-bottomed flasks, then heating reflux reaction 6 hours,
Stop heating, is down to room temperature, suitable distilled water is added, filters out solid.In methylene chloride by solid dissolution, it is short to cross silica gel
Column.Remove solvent at reduced pressure conditions, the solid being concentrated to get successively uses methanol and petroleum ether, obtain 2.2 grams (yield:
68%) required product.LC-MS:M/Z 849.2(M+H)+
The synthesis of 15.RD-362
Dichloro is crosslinked 3 grams of Dimer Complex (1.9mmol), 3,7- 1.2 grams of diketone of diethyl -5- methyl -4,6- nonyls
(5.7mmol), in 1.2 grams of natrium carbonicum calcinatum (11.5mmol) and cellosolvo 80ml addition twoport round-bottomed flasks, then
Heating reflux reaction 6 hours, stops heating, be down to room temperature, suitable distilled water is added, filters out solid.Solid is dissolved in
In methylene chloride, short column of silica gel is crossed.Solvent is removed at reduced pressure conditions, and the solid being concentrated to get successively is washed with methanol and petroleum ether
It washs, obtains 2.4 grams of (yields: 66%) required product.LC-MS:M/Z 961.4(M+H)+
16. the synthesis that dichloro is crosslinked the synthesis of Dimer Complex
By 3 grams of monohydrate (10mmol) of iridous chloride, 5- isobutyl group -2- (3,5- dimethyleyelohexane -1- alkene -1- base)
The ratio of 6.5 grams of quinoline (22.1mmol) and diethanol list ether and distilled water is
The mixed solution of 3/1 (120mL/40mL) is added in two mouthfuls of dry round-bottomed flasks, and heating reflux reaction 24 is small
When, then it is added suitable distilled water, then the solid of precipitation is filtered, and with methanol and petroleum ether solid, obtain 5.0 grams
(yield: 61%) dichloro is crosslinked Dimer Complex.
LC-MS:M/Z 1626.1 (M+H)+
The synthesis of 17.RD-006
By dichloro be crosslinked 3 grams of Dimer Complex (1.8mmol), 0.9 gram of pentane -2,4- diketone (9.2mmol), anhydrous carbon
Sour sodium 1.2 grams (11.1mmol) and cellosolvo 80ml are added in twoport round-bottomed flask, and then heating reflux reaction 6 is small
When, stop heating, is down to room temperature, suitable distilled water is added, filters out solid.In methylene chloride by solid dissolution, silicon is crossed
Glue short column.Solvent is removed at reduced pressure conditions, and the solid being concentrated to get successively uses methanol and petroleum ether, obtains 2.1 grams and (receives
Rate: 66%) required product.LC-MS:M/Z 877.2(M+H)+
The synthesis of 18.RD-366
Dichloro is crosslinked 3 grams of Dimer Complex (1.8mmol), 3,7- 1.2 grams of diketone of diethyl -5- methyl -4,6- nonyls
(5.5mmol), in 1.2 grams of natrium carbonicum calcinatum (11.1mmol) and cellosolvo 80ml addition twoport round-bottomed flasks, then
Heating reflux reaction 6 hours, stops heating, be down to room temperature, suitable distilled water is added, filters out solid.Solid is dissolved in
In methylene chloride, short column of silica gel is crossed.Solvent is removed at reduced pressure conditions, and the solid being concentrated to get successively is washed with methanol and petroleum ether
It washs, obtains 2.3 grams of (yields: 64%) required product.LC-MS:M/Z 989.4(M+H)+
Embodiment
1. first embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, patterned ito glass is washed
Substrate.The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBCBP+RD-001 (5%)Alq3 And AlIt is suitable
The layer of sequence formation organic substance.
At 0.9 ma, brightness is equal to 1248cd/m2(5.8V).At this point, CIEx=0.641, y=0.356.
2. the second embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.It is washed out patterned ito glass
Substrate.The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBCBP+RD-361 (5%)Alq3 LiFAnd AlIt is suitable
The layer of sequence formation organic substance.
At 0.9 ma, brightness is equal to 1293cd/m2(6.0V).At this point, CIEx=0.644, y=0.352.
3. third embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, patterned ito glass is washed
Substrate.The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBCBP+RD-002 (5%)Alq3 LiFAnd AlIt is suitable
The layer of sequence formation organic substance.
At 0.9 ma, brightness is equal to 1261cd/m2(5.7V).At this point, CIEx=0.645, y=0.349.
4. the 4th embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, patterned ito glass is washed
Substrate.The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBCBP+RD-362 (5%)Alq3 LiFAnd AlIt is suitable
The layer of sequence formation organic substance.
At 0.9 ma, brightness is equal to 1339cd/m2(6.0V).At this point, CIEx=0.648, y=0.345.
5. the 5th embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, patterned ito glass is washed
Substrate.The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBCBP+RD-006 (5%)Alq3 LiFAnd AlIt is suitable
The layer of sequence formation organic substance.
At 0.9 ma, brightness is equal to 1312cd/m2(5.9V).At this point, CIEx=0.651, y=0.341.
6. the 6th embodiment
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, patterned ito glass is washed
Substrate.The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.Hereafter, on an ito substrate with CuPcNPBCBP+RD-366 (5%)Alq3 LiFAnd AlIt is suitable
The layer of sequence formation organic substance.
At 0.9 ma, brightness is equal to 1358cd/m2(6.2V).At this point, CIEx=0.653, y=0.339.
7. comparative example
Pattern ito glass substrate, with the light emitting region with 3mm × 3mm.Then, patterned ito glass is washed
Substrate.The substrate is then placed in vacuum chamber.Normal pressure is set as 1 × 10-6Support.On an ito substrate with CuPcNPBCPB+(btp)2Ir (acac) (5%)Alq3 LiFAnd AlThe layer for sequentially forming organic substance.
When forming a hole support layer using baiq, at 0.9 ma, brightness is equal to 689cd/m2(8.1V).At this point, CIEx
=0.651, y=0.329
The characteristic of foundation the embodiment above and comparative example, efficiency, chromaticity coordinate and brightness is shown in the following table 1.
Table 1
As shown in table 1, or even when excitation purity is high, which also expeditiously runs at low voltage.Further, with comparison
Example is compared, and the current efficiency of the second embodiment increases by 100% or more.By using 1 compound represented of formula as Organic Electricity
The luminescent layer of electroluminescence device, the present invention provide the organic electroluminescence with excellent excitation purity and brightness and extended durability
Luminescent device.
Those skilled in the art will be, it is evident that without departing from the spirit and scope of the invention, the present invention can have
Many modifications and variations.Therefore it is desired that arriving, the present invention is covered in the range and its suitable range of accessory claim and mentions
The modifications and variations of the invention supplied.
Claims (7)
1. a kind of red phosphorescent compound, it is characterised in that: shown in its structural formula as I,
Wherein,It indicates
Wherein, R1, R2, R3 and R4 are independently selected from H, C1~C6 alkyl one kind；
And wherein,Show alkane diketone and its derivative chosen from the followings:
2. the red phosphorescent compound according to claim 1, it is characterised in that: C1~C6 alkyl is selected from methyl, methyl-
D3, ethyl, n-propyl, isopropyl, normal-butyl, one of isobutyl group and tert-butyl.
3. the red phosphorescent compound according to claim 1, which is characterized in that whereinIt is in following chemical formula
Any one:
4. the red phosphorescent compound in -3 according to claim 1, it is characterised in that: the red phosphorescent compound is selected from following
Chemical formula:
5. a kind of organic light emitting diode device, it is characterised in that: the device includes the anode being sequentially deposited each other, hole note
Enter layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode；The organic electroluminescence device includes power
Benefit requires in 1-4 any compound as dopant.
6. organic electroluminescent diode component according to claim 5, it is characterised in that: the Organic Light Emitting Diode device
Any one of Al or Zn metal complex and carbazole derivates are used to adulterate in part as the material of main part of luminescent layer, and wherein
The amount ranges of agent are within the scope of 0.1 weight of weight %~50 %.
7. according to the organic electroluminescent diode component in claim 5, it is characterised in that: Al the or Zn metal complex
Ligand is quinolyl, in xenyl, isoquinolyl, phenyl, methylquinoline base, dimethyl quinoline base, dimethyl-isoquinolyl
It is one or more of；The carbazole derivates are 4,4 '-N, N the click biphenyl of '-two.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811026991.5A CN109206458A (en) | 2018-09-04 | 2018-09-04 | Red phosphorescent compound and the organic light emitting diode device for using the compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811026991.5A CN109206458A (en) | 2018-09-04 | 2018-09-04 | Red phosphorescent compound and the organic light emitting diode device for using the compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109206458A true CN109206458A (en) | 2019-01-15 |
Family
ID=64986739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811026991.5A Pending CN109206458A (en) | 2018-09-04 | 2018-09-04 | Red phosphorescent compound and the organic light emitting diode device for using the compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109206458A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020094453A1 (en) * | 2000-11-29 | 2002-07-18 | Takao Takiguchi | Metal coordination compound, luminescence device and display apparatus |
| US20070259207A1 (en) * | 2006-05-08 | 2007-11-08 | Canon Kabushiki Kaisha | Metal complex, light-emitting device, and image display apparatus |
| CN101607973A (en) * | 2007-11-20 | 2009-12-23 | 葛来西雅帝史派有限公司 | New organic electroluminescent compounds and use the el light emitting device of this compound |
| CN101665521A (en) * | 2008-01-29 | 2010-03-10 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN101747888A (en) * | 2008-12-01 | 2010-06-23 | 乐金显示有限公司 | Red phoshorescent compound and organic electroluminescent device using the same |
| CN102264864A (en) * | 2008-10-29 | 2011-11-30 | 葛来西雅帝史派有限公司 | Novel compounds for electronic material and organic electronic device using same |
-
2018
- 2018-09-04 CN CN201811026991.5A patent/CN109206458A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020094453A1 (en) * | 2000-11-29 | 2002-07-18 | Takao Takiguchi | Metal coordination compound, luminescence device and display apparatus |
| US20070259207A1 (en) * | 2006-05-08 | 2007-11-08 | Canon Kabushiki Kaisha | Metal complex, light-emitting device, and image display apparatus |
| CN101607973A (en) * | 2007-11-20 | 2009-12-23 | 葛来西雅帝史派有限公司 | New organic electroluminescent compounds and use the el light emitting device of this compound |
| CN101665521A (en) * | 2008-01-29 | 2010-03-10 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN102264864A (en) * | 2008-10-29 | 2011-11-30 | 葛来西雅帝史派有限公司 | Novel compounds for electronic material and organic electronic device using same |
| CN101747888A (en) * | 2008-12-01 | 2010-06-23 | 乐金显示有限公司 | Red phoshorescent compound and organic electroluminescent device using the same |
Non-Patent Citations (1)
| Title |
|---|
| DONG MIN KANG等，: "Iridium Complexes with Cyclometalated 2-Cycloalkenyl-Pyridine Ligands as Highly Efficient Emitters for Organic Light-Emitting Diodes", 《ADV. MATER.》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1783133B1 (en) | Red phosphorescent compound and organic electroluminescent device using the same | |
| KR20140024439A (en) | Novel organic electroluminescent compounds and organic electroluminescent device using the same | |
| CN110467630A (en) | A kind of phosphorescent compound and the organic light emitting diode device using the compound | |
| CN110452271A (en) | Red phosphorescent compound and the organic electroluminescence device for using the compound | |
| CN110746401A (en) | Phosphorescent compound and organic light emitting diode device using the same | |
| CN108997438B (en) | Red phosphorescent compound and organic light emitting diode device using the same | |
| CN111153888A (en) | Phosphorescent compound and organic light emitting diode device using the same | |
| CN109988193A (en) | Green phosphorescent compound and the organic electroluminescence device for using the compound | |
| CN110903300A (en) | Phosphorescent compound and organic light emitting diode device using the same | |
| CN112500395B (en) | Dibenzo nitrogen-containing seven-membered heterocyclic organic compound, preparation method thereof and organic electroluminescent device | |
| CN111116673A (en) | Red phosphorescent compound and organic electroluminescent device using the same | |
| CN110872301A (en) | Phosphorescent compound and organic light emitting diode device using the same | |
| KR20090032250A (en) | Red phosphorescence compound and organic electroluminescence device using the same | |
| CN109810146A (en) | Green phosphorescent compound and the organic electroluminescence device for using the compound | |
| CN110724168A (en) | Red phosphorescent compound and organic electroluminescent device using the same | |
| CN109206457A (en) | Red phosphorescent compound and the organic electroluminescence device for using the compound | |
| KR101799033B1 (en) | Red color phosphorescent host material and Organic electroluminescent display device using the same | |
| CN110467642A (en) | Red phosphorescent compound and the organic electroluminescence device for using the compound | |
| CN109988192A (en) | Green phosphorescent compound and the organic electroluminescence device for using the compound | |
| KR20120036560A (en) | Red color phosphorescent host material and organic electroluminescent display device using the same | |
| CN109206458A (en) | Red phosphorescent compound and the organic light emitting diode device for using the compound | |
| CN109776616A (en) | Green phosphorescent compound and the organic electroluminescence device for using the compound | |
| CN110938097A (en) | Green phosphorescent compound and organic electroluminescent device using the same | |
| CN109232656A (en) | Red phosphorescent compound and the organic electroluminescence device for using the compound | |
| CN109485678A (en) | Red phosphorescent compound and the organic electroluminescence device for using the compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190115 |