CN107353309A - A kind of metal complex, synthetic method and its application in organic electroluminescence device - Google Patents

A kind of metal complex, synthetic method and its application in organic electroluminescence device Download PDF

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CN107353309A
CN107353309A CN201710568885.9A CN201710568885A CN107353309A CN 107353309 A CN107353309 A CN 107353309A CN 201710568885 A CN201710568885 A CN 201710568885A CN 107353309 A CN107353309 A CN 107353309A
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substituted
layer
unsubstituted
metal complex
organic
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孙可
孙可一
蔡辉
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Changchun Haipurunsi Technology Co Ltd
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    • 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
    • C07F15/0086—Platinum compounds
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    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • 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
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a kind of metal complex, synthetic method and its application in organic electroluminescence device, the formula of the metal complex is：Wherein, R1Selected from substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C60Alkoxy, substituted or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical；L is selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substituted or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical.Organic electroluminescence device prepared by metal complex of the present invention can the limited solution luminescent properties difference such as organic photoelectrical material luminous efficiency is low in the prior art, driving voltage is higher, service life is short technical problem.

Description

A kind of metal complex, synthetic method and its in organic electroluminescence device Using
Technical field
The present invention relates to organic photoelectrical material technical field.More particularly to a kind of metal complex, synthetic method and its Application in organic electroluminescence device.
Background technology
In general organic luminescent device (OLED) is the organic matter layer structure by being inserted between negative electrode, anode and negative electrode and anode Into, the composition of device is transparent ITO anode, hole injection layer (HIL), hole transmission layer (HTL), luminescent layer (EL), hole The negative electrodes such as barrier layer (HBL), electron transfer layer (ETL), electron injecting layer (EIL), Li/Al are formed, on demand can clipped Organic layer.Voltage is formed between two electrodes of device, while being injected from cathode electronics, another side anode injection hole.Electronics Return to stable ground state in conjunction with excitation state, excitation state is formed in luminescent layer with hole and produce luminescence phenomenon.Luminescent material is divided into Fluorescent material and phosphor material, the forming method of luminescent layer are that the side of phosphor material (organic metal) is adulterated in fluorescent host material The method of method and fluorescent host material doping fluorescent.Emission wavelength can be improved by such mix, efficiency, driving voltage, The factors such as life-span.
Generally forming emitting layer material has the centerbodies such as benzene, naphthalene, fluorenes, the fluorenes of spiral shell two, anthracene, pyrene, carbazole；Benzene, biphenyl, naphthalene, The parts such as heterocycle；The replacing structure such as contraposition, meta, the binding site at ortho position and amido, cyano group, fluorine, methyl, the tert-butyl group.
In OLED, there is variform in organometallic ligand.Cyan luminescent material has FIrPic and Bepp2, green Luminescent material has Zn (BTZ) 2 and Alq3, electron transport material material have Alq3, electron injection material have Liq etc..
At this stage also there is blue-light device stability problem in blue light emitters (emitter) application aspect.
As oled panel development is progressively maximized, industry needs the finer and smoother and distincter material of color, wherein solving Emphasis be blue material, especially need light blue to arrive navy blue high performance material.On the other hand, low driving voltage, height Efficiency light emission efficiency and the good high glass transition temperature material of heat endurance are also needed for industry.
The content of the invention
This designs metal complex by the way of organic ligand and a metallic atom coordination.The metal complex can To improve excitation, improve intermolecular stability and luminous efficiency.Can using the organic electroluminescence device of the metal complex To apply (emitter) and photon converter technique (photon down-converter) etc. in terms of organic luminescent device, illumination Aspect.
The invention provides a kind of luminous organic material of metal complex, its molecular structural formula is：
[chemical formula 1]
Wherein, R1Selected from substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C60Alkoxy, substitution Or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical；L is selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substitution or non- Substitute C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical.
Preferably, R1Selected from substituted or unsubstituted C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substitution Or non-substituted C6~C30Aryl, substituted or non-substituted C5~C30Heterocyclic radical, substituted or non-substituted C5~C30Condensed ring radical；L be selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substitution or non-taken For C6~C30Aryl, substituted or non-substituted C5~C30Base, substituted or non-substituted C5~C30Condensed ring radical.
Preferably, described golden chemical formula 1 is as shown in any one in following chemical formula 2-1~chemical formula 2-3：
[chemical formula 2-1]
[chemical formula 2-2]
[chemical formula 2-3]
Wherein, R1Selected from substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C60Alkoxy, substitution Or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical；L is selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substitution or non- Substitute C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical.
Preferably, M is selected from Pt metal
Preferably, any one of described metal complex in following chemical constitution：
Present invention also offers a kind of organic luminescent device, including first electrode, second electrode and it is placed in two electrode Between one or more organic compound layers, it is at least one layer of in the organic compound layer to match somebody with somebody comprising metal of the present invention Compound.
Preferably, the organic compound layer includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, sky At least one layer in cave barrier layer, electron transfer layer, electron injecting layer.
Preferably, organic luminescent device of the present invention, illumination, Display panel, organic photovoltaic cell, electricity be can be applied to The fields such as sub- paper, Organophotoreceptor or OTFT.
Beneficial effects of the present invention：
The invention provides a kind of luminous organic material and its organic luminescent device of new metal complex, the material with Metal ligand compound is agent structure, by connecting the ligand groups of opposed polarity, can adjust the pi-conjugated property of material, band gap Width, electrophilicity, charge transport ability and photochromic etc. so that metal ligand compound of the invention has relatively low band gap width, Higher luminous efficiency, electronic transmission performance, membrane stability and heat endurance.The organic luminescent device energy prepared using the present invention Effectively solve the problems, such as that blue light material electron injection rate is low, overcome the unbalanced problem of conventional unipolar luminescent material carrier, So that device has higher luminous efficiency, outstanding chemical property and thermal stability.
Embodiment：
It is clearly and completely described below in conjunction with the technical scheme of the embodiment of the present invention, it is clear that described implementation Example is only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects Enclose.
The invention provides a kind of luminous organic material of new metal complex structure, its molecular structural formula are as follows：
[chemical formula 1]
Wherein, R1Selected from substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C60Alkoxy, substitution Or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical；L is selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substitution or non- Substitute C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical.
Preferably, R1Selected from substituted or unsubstituted C1~C20Alkyl, substituted or unsubstituted C1~C20Alkoxy, substitution Or non-substituted C6~C30Aryl, substituted or non-substituted C5~C30Heterocyclic radical, substituted or non-substituted C5~C30Condensed ring radical；L be selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substitution or non-taken For C6~C30Aryl, substituted or non-substituted C5~C30Base, substituted or non-substituted C5~C30Condensed ring radical.Further preferably, the R1 Selected from C1-C10 alkyl, C6-C18 aryl, it is furthermore preferred that the R4Selected from methyl or phenyl.
According to the present invention, the substituted alkyl, substitution alkoxy, substitution aryl, substitution heterocyclic radical, substitution In condensed ring radical, the substituent may be selected from deuterium or C1-C10Alkyl.Hetero atom is preferably N, O or S described in the heterocyclic radical.
Preferably, any one institute in described metal complex chemical formula 1 such as following chemical formula 2-1~chemical formula 2-3 Show：
[chemical formula 2-1]
[chemical formula 2-2]
[chemical formula 2-3]
Wherein, R1Selected from substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C60Alkoxy, substitution Or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical；L is selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substitution or non- Substitute C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical.
Preferably, organometallic complex of the present invention, M Pt.
Preferably, any one of described metal complex in following chemical constitution：
Present invention also offers a kind of organic luminescent device, including first electrode, second electrode and it is placed in two electrode Between one or more organic compound layers, the organic compound layer is at least one layer of metal combination of the present invention Thing.
Organic matter layer of the present invention wherein at least include hole injection layer, hole transmission layer, not only possessed hole injection but also Possess hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and both possessed Electric transmission is but also with least one layer in electron injection technical ability layer.
Above-mentioned hole injection layer, hole transmission layer, both possessed hole injection but also with hole transport technical ability layer at least one It is individual to be conventional hole injecting material, hole transporting material and both possess hole injection but also with hole transport technical ability material, It is likely to be the material of electron-transporting material generation.
" organic matter layer " refers to the whole disposed between organic electronic device first electrode and second electrode in this patent The term of layer.
For example above-mentioned organic layer includes luminescent layer, above-mentioned organic layer includes phosphorescence host, fluorescent host, phosphorescence doping And more than one in fluorescence doping, wherein above-mentioned luminescent layer includes above-mentioned new metal ligand：I) above-mentioned fluorescent host can be Above-mentioned new metal ligand；Ii) above-mentioned fluorescence doping can be above-mentioned new metal ligand；Ii i) above-mentioned fluorescent host and glimmering Photodoping can be above-mentioned new metal ligand.
It can also be red, yellow or cyan luminescent layer that above-mentioned luminescent layer, which is,.For example above-mentioned luminescent layer is when being cyan, on State new metal ligand and use cyan main body or cyan object.
Above-mentioned organic layer includes electron transfer layer, and electron transfer layer includes above-mentioned new metal ligand.Wherein above-mentioned electricity Sub- transport layer is to include the compound containing other metals beyond above-mentioned new metal ligand again.
Above-mentioned organic layer all includes luminescent layer and electron transfer layer, and above-mentioned luminescent layer and electron transfer layer each include above-mentioned New metal ligand (above-mentioned luminescent layer and electron transfer layer include above-mentioned new metal ligand can also it is identical can not also Together).
Above-mentioned organic electronic device is using the described new becket part of chemical formula 1 with conventional material and preparation method Prepare.
Another aspect of the present invention is that above-mentioned device can be used in organic luminescent device (OLED), organic photovoltaic cell (OSC), Electronic Paper (e-Paper), Organophotoreceptor (OPC) or OTFT (OTFT).
Organic luminescent device is to be deposited using the methods of film vapor deposition, electron beam evaporation, physical vapour deposition (PVD) on substrate Metal and conductive oxide and their alloy form anode.Its above-mentioned hole injection layer, hole are passed on layer, lighted Layer, hole blocking layer and electron transfer layer preparation method enter above-mentioned shown.
Above-mentioned organic matter layer is can also to include hole injection layer, hole reception and registration layer, luminescent layer, hole blocking layer and electronics The sandwich constructions such as transport layer, and above-mentioned organic matter layer is to substitute evaporation coating method using various high polymer material solvent engineering, Such as spin-coating (spin-coating), strip shaping (tape-casting), scraping blade method (doctor-blading), silk The methods of wire mark brush (Screen-Printing), ink jet printing or thermal imaging (Thermal-Imaging), reduces number of plies manufacture.
The method that the present invention prepares new metal complex, comprises the following steps：
Step 1, according to the method that ligand (A) is prepared the methods of coupling reaction, aminating reaction, reduction reaction；
Step 2, it is to include ligand (A) and metal salt, halide with the new metal complex of acetic acid cooperation acquisition as follows Method.
The present invention does not have particular/special requirement to the condition of above-mentioned all kinds of reactions, is such reaction well known to those skilled in the art Normal condition, wherein R1, L, M selection it is same as above, will not be repeated here.
Prompting another aspect of the present invention is to provide the preparation method of above-mentioned new metal ligand, but example below below It is to understand that present disclosure provides, the content of the invention is not limited to this scope.
[embodiment 1] compound 3-1 synthesis
* intermediate 3-1-A preparation
By 3- benzaldehyde iodines (4.64,20mmol), N- methyl-o-PDA (2.44,20mmol), sodium pyrosulfite (5.73g, 30mmol), dimethylformamide 200ML are added in reaction bulb, are heated to backflow overnight.Cooling, reaction solution is fallen Enter to 500ML cold water, do not stop to stir, there is solid precipitation.Alcohol flushing is first used, then is rinsed with petroleum ether, finally dry 3-1-A (3.91g, 80%).
* intermediate 3-1-B preparation
By m-hydroxybenzaldehyde (2.44,20mmol), N- methyl-ortho-phenylene diamine (2.44,20mmol), sodium pyrosulfite (5.73g, 30mmol), dimethylformamide 200ML are added in reaction bulb, are heated to backflow overnight.Cooling, reaction solution is fallen Enter to 500ML cold water, do not stop to stir, there is solid precipitation.Alcohol flushing is first used, then is rinsed with petroleum ether, finally dry 3-1-B (3.36g, 75%).
* intermediate 3-1-C preparation
In reaction vessel under condition of nitrogen gas plus 3-1-A (3.42g, 10.24mmol), 3-1-B (2.09g, 9.31mmol), CuI (I) (0.532g, 2.79mmol), dimethyl sulfoxide (DMSO)Pyridine carboxylic acid (1.7g, 13.96mmol) and potassium phosphate (6.9g,32.6mmol).24h is stirred at a temperature of 105 DEG C of reaction condition.Add ethyl acetate diluting reaction thing after reactant cooling It is filtrated to get organic layer later.Vacuum distillation remove after solvent with silicon gel column purify to obtain compound 3-1-C (1.20g, 30%).
* compound 3-1 preparation
Add 3-1-C (3.36g, 7.80mmol), Platinous Potassium Chloride (3.24g, 7.8mmol), glacial acetic acid in reaction vessel Later return stirring 68h, after reactant cooling plus water 50mL obtains solid matter.Solid matter dichloromethane Organic layer is washed with water after dissolving, organic layer is dried with MgSO4.Vacuum distillation is purified after removing solvent with silicon gel column To compound 3-1 (2.43g, 50%).
[embodiment 2] compound 3-2 synthesis
* intermediate 3-2-A preparation
By 3- nitrobenzaldehydes (3.02,20mmol), N- methyl-o-PDA (2.44,20mmol), sodium pyrosulfite (5.73g, 30mmol), dimethylformamide 200ML are added in reaction bulb, are heated to backflow overnight.Cooling, reaction solution is fallen Enter to 500ML cold water, do not stop to stir, there is solid precipitation.Alcohol flushing is first used, then is rinsed with petroleum ether, finally dry 3-2-A (3.80g, 75%).
* embodiment 3-2-B preparation
3-2-A (5.06g, 20mmol), absolute ethyl alcohol, and appropriate palladium-carbon catalyst are added in reaction vessel, in hydrogen gas Under atmosphere, 24h is reacted at room temperature.Celite pillars are crossed after the completion of reaction.It is spin-dried for solvent and obtains 3-2-B (4.15g, 93%).
* intermediate 3-2-C preparation
3-1-B (57.1mmol, 12.75g), 3-1-A (68.5mmol, 22.89g) add 250mL there-necked flasks, add under nitrogen Enter three (dibenzalacetone) double palladiums (1.7mmol, 0.98g), tert-butyl group sodium alkoxide (114.2mmol, 11g), toluene 100mL, often After temperature stirring 30min, tri-butyl phosphine (11.4mmol, 2.3g) is added under nitrogen protection and is warming up to 80 DEG C of reaction 20h.After locate Reason：Extraction, organic phase recrystallized after being evaporated with petroleum ether, and crude product crossed into column chromatography, eluant, eluent with petroleum ether/dichloromethane= 5:Organic phase is evaporated rear product 3-2-C (14.22g, 58%) by 1.
* intermediate 3-2-D preparation
Add 3-5-C (10.78g, 25.1mmol), tetrahydrofuran (100mL), low temperature (0 under condition of nitrogen gas in reaction vessel DEG C) under plus hydrogenated sodium (0.7g, 27.6mmol) stir 1h later, then iodomethane 1.72ml, 27.6mmol is slowly added dropwise) after stir 2h is mixed, normal temperature is stirred for 1h.Organic layer separation is dried with MgSO4.Vacuum distillation is purified after removing solvent with silicon gel column To compound 3-2-D (10.58g, 95%).
* compound 3-2 preparation
Add 3-2-D (3.46g, 7.80mmol), Platinous Potassium Chloride (3.24g, 7.8mmol), glacial acetic acid in reaction vessel Later return stirring 68h, after reactant cooling plus water 50mL obtains solid matter.Solid matter dichloromethane Organic layer is washed with water after dissolving, organic layer is dried with MgSO4.Vacuum distillation is purified after removing solvent with silicon gel column To compound 3-2 (2.48g, 50%).
[embodiment 3] compound 3-3 synthesis
* intermediate 3-3-A preparation
3-1-A (28.33g, 84.77mmol) is dissolved in tetrahydrofuran (500mL) cools down -78 DEG C later after and is slowly added dropwise N-BuLi (2.5M/33.9mL, 84.77mmol) stirs 1h later.The dimethyl for being dissolved in tetrahydrofuran (50mL) is slowly added dropwise Dichlorosilane (4.92g, 38.14mmol).12h is stirred under normal temperature condition, organic matter is extracted with ethyl acetate, organic layer is used MgSO4 is dried.Vacuum distillation is purified to obtain compound 3-3-A (10.02g, 60%) after removing solvent with silicon gel column.
* compound 3-3-A preparation
Add 3-3-A (3.69g, 7.80mmol), Platinous Potassium Chloride (3.24g, 7.8mmol), glacial acetic acid in reaction vessel Later return stirring 68h, after reactant cooling plus water 50mL obtains solid matter.Solid matter dichloromethane Organic layer is washed with water after dissolving, organic layer is dried with MgSO4.Vacuum distillation is purified after removing solvent with silicon gel column To compound 3-3 (2.33g, 45%).
Device prepares embodiment 1：
It is by Fisher Co., Ltd's coating layer thicknessIto glass substrate be placed in distilled water and clean 2 times, ultrasonic wave is washed Wash 30 minutes, cleaned repeatedly with distilled water 2 times, ultrasonic washing 10 minutes, after distilled water cleaning terminates, isopropanol, acetone, first Alcohol equal solvent in order dry later by ultrasonic washing, is transferred in plasma washing machine, aforesaid substrate is washed 5 minutes, It is sent in evaporator.
Hole injection layer CuPc/10nm, evaporation hole transmission layer a- will be deposited on the ito transparent electrode being already prepared to NPD/40nm, evaporation main body CBP：Doping RD1 or above example compound 6% mix/and 35nm and then electronic shell be each deposited BAlq/10nm and Alq3/ 35nm, negative electrode LiF/0.5nm, Al/100nm.
The electron luminescence characteristic of the organic luminescent device of above method manufacture represents in table 1.
The electron luminescence characteristic of the luminescent device of table 1
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The present invention is the organic electroluminescence device prepared using described metal complex, can obtain luminous efficiency and Life-span good result, so the present invention has higher practicality in OLED industries.The organic luminescent device of the present invention is flat Faceplate panels are shown, planar illuminant, illumination face illuminating OLED illuminator, flexible illuminator, duplicator, printer, LCD backlight The field such as lamp or the light source of dosing machine class, display board, mark can widely use.

Claims (10)

1. a kind of metal complex, it is characterised in that the metal complex general molecular formula is：
[chemical formula 1]
Wherein, R1Selected from substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C60Alkoxy, substitution or non- Substitute C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical；L be selected from O, S, Substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substituted or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical.
2. metal complex according to claim 1, it is characterised in that R1Selected from substituted or unsubstituted C1~C20Alkyl, Substituted or unsubstituted C1~C20Alkoxy, substituted or non-substituted C6~C30Aryl, substituted or non-substituted C5~C30Heterocyclic radical, take Generation or non-substituted C5~C30Condensed ring radical；L is selected from O, S, substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substituted or non-substituted C6~C30Aryl, substituted or non-substituted C5~C30It is base, substituted or non-substituted C5~C30Condensed ring radical.
3. metal complex according to claim 1, it is characterised in that described chemical formula 1 such as following chemical formula 2-1~ Shown in any one in chemical formula 2-3：
[chemical formula 2-1]
[chemical formula 2-2]
[chemical formula 2-3]
Wherein, R1Selected from substituted or unsubstituted C1~C30Alkyl, substituted or unsubstituted C1~C60Alkoxy, substitution or non- Substitute C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical；L be selected from O, S, Substituted or unsubstituted amido, substituted or unsubstituted silylation；M is selected from Pt, Pd, Ir, R or Au；A is selected from substituted or non-substituted C6~C60Aryl, substituted or non-substituted C5~C60Heterocyclic radical, substituted or non-substituted C5~C60Condensed ring radical.
4. metal complex according to claim 1, it is characterised in that described M is selected from Pt metal.
5. metal complex according to claim 1, it is characterised in that any one in following chemical constitution：
6. metal complex according to claim 1, it is characterised in that the ligand preparation side of described metal complex Method includes：Coupling reaction, aminating reaction, reduction reaction method；Preparing the method for ligand includes：Ligand and metal salt coordination Stage, halide coordinate the stage for obtaining mixture with acetic acid；The blend heated stage；The stage of mixture room temperature cooling.
7. metal complex according to claim 5, it is characterised in that described metal salt is K2PtCl4。
8. a kind of organic electroluminescence device, including first electrode, second electrode and one be placed between two electrode or Multiple organic compound layers, it is characterised in that at least one layer of any one comprising Claims 1 to 4 in the organic compound layer Metal complex described in.
9. organic electroluminescence device according to claim 7, it is characterised in that the organic matter layer injects including hole Layer, hole transmission layer, both possessed hole injection but also with hole transport technical ability layer, electronic barrier layer, luminescent layer, hole barrier Layer, electron transfer layer, electron injecting layer and both possesses electric transmission but also with least one layer in electron injection technical ability layer.
10. organic electroluminescence device according to claim 7, it is characterised in that described organic electroluminescence device For organic luminescent device, organic photovoltaic cell, Electronic Paper, Organophotoreceptor or OTFT.
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