CN107936951A - A kind of organic luminescent compounds and its organic electroluminescence device - Google Patents
A kind of organic luminescent compounds and its organic electroluminescence device Download PDFInfo
- Publication number
- CN107936951A CN107936951A CN201711122682.3A CN201711122682A CN107936951A CN 107936951 A CN107936951 A CN 107936951A CN 201711122682 A CN201711122682 A CN 201711122682A CN 107936951 A CN107936951 A CN 107936951A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- substituted
- organic
- compound
- luminescent compounds
- 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.)
- Withdrawn
Links
- 0 CCC1=*CC(C(C(C=C2)=C3C4=CC(C5)CC(CC=C(C(C6)C(C=C7)*(C)=N8)C(c9ccc(**C)cc9)(C(CC=C9)=Cc%10c9nccc%10)NC9(C)CC8=CC=CC9)C6=C7C2=C5C3)(C(C=C2)=CC3c5c2nccc5)[n]2c4nc4cccc3c24)C=C1 Chemical compound CCC1=*CC(C(C(C=C2)=C3C4=CC(C5)CC(CC=C(C(C6)C(C=C7)*(C)=N8)C(c9ccc(**C)cc9)(C(CC=C9)=Cc%10c9nccc%10)NC9(C)CC8=CC=CC9)C6=C7C2=C5C3)(C(C=C2)=CC3c5c2nccc5)[n]2c4nc4cccc3c24)C=C1 0.000 description 6
- ZJMWRROPUADPEA-UHFFFAOYSA-N CCC(C)c1ccccc1 Chemical compound CCC(C)c1ccccc1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N N#Cc1ccccc1 Chemical compound N#Cc1ccccc1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed systems contains four or more hetero rings
-
- 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
- H10K50/16—Electron transporting 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
Abstract
The invention discloses a kind of organic luminescent compounds and its organic electroluminescence device, and the present invention relates to organic photoelectrical material technical field.It is an advantage of the invention that, the organic luminescent compounds of the present invention are the aromatic series organic molecule with big plane, its conjugated system is larger, therefore has higher electron mobility, in addition organic luminescent compounds of the invention also have preferable heat endurance and dissolubility, are conducive to material filming；Using organic electroluminescence device of the organic luminescent compounds of the present invention as organic matter layer, there are relatively low driving voltage, higher luminous efficiency and luminous brightness, and there is longer service life.
Description
Technical field
The present invention relates to organic photoelectrical material technical field, and in particular to a kind of organic luminescent compounds and its organic electroluminescence
Luminescent device.
Background technology
OLED (Organic Light-Emitting Diode, organic electroluminescence device) is flat as a new generation in recent years
Plate is shown and solid state lighting technology just receives more and more attention.OLED refers to organic photoelectrical material in electric current or the work of electric field
With lower luminous device, electric energy can be converted into luminous energy by it.Compared to LCD technology, OLED with its low-power consumption,
Actively luminous, fast response time, high contrast, no angle limit, can make the features such as Flexible Displays, be increasingly used in
Display and lighting area.
OLED is a kind of sandwich of sandwich style, i.e. organic photoelectrical material is clipped in the centre of cathode and anode.Foundation
Organic photoelectrical material performance different performance, can be classified as electron injection material, electron transport material, hole barrier materials,
Subjective and Objective luminescent material, electron-blocking materials, hole mobile material and hole-injecting material.In general, using has low work function
Alkali metal as cathode, anode is used as using transparent tin indium oxide (ITO).The structure of OLED can be divided into substantially individual layer,
Double-deck, three layers and multilayer device structure, according to the difference of material therefor property, on demand can be adjusted the structure of device.
For the electron transport material in OLED, refer to can to control under electric field action the oriented and ordered migration of electronics so as to
Realize the organic semiconducting materials of electric transmission, its basic role is to improve electronics efficiency of transmission in the devices, and by hole
Effectively it is blocked in luminescent layer, realizes the maximum compound of carrier, so that it is guaranteed that OLED has relatively stable performance.
At present, the hole mobility applied to the hole mobile material in OLED is typically much deeper than the electricity of electron transport material
Transport factor, this can directly result in being remarkably decreased for OLED performances.It is embodied in, operation voltage is high, luminous efficiency is low, uses
The problems such as short life, therefore, design the electron transport material with excellent performance with stronger realistic meaning.
The content of the invention
Goal of the invention：In view of the above-mentioned problems, the object of the present invention is to provide a kind of organic luminescent compounds and its Organic Electricity
Electroluminescence device, which applies in organic electroluminescence device as electron transport material, so as to reduce Organic Electricity
The driving voltage of electroluminescence device, improves the luminous efficiency of organic electroluminescence device, and extends organic electroluminescent
The service life of device.
The above-mentioned technical purpose of the present invention is achieved through the following technical solutions：A kind of organic luminescent compounds, the change
Compound has the general structure as shown in structural formula I：
Wherein, R1、R2、R3、R4The independent alkyl selected from substituted or unsubstituted C1~C60, substituted or unsubstituted C6
The aryl of~C60, substituted or unsubstituted C3~C60 heteroaryl in one kind.
Preferably, R1、R2、R3、R4It is the independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted
The aryl of C6~C30, substituted or unsubstituted C3~C30 heteroaryl in one kind.
Most preferably, R1、R2、R3、R4Independent is selected from methyl, ethyl, propyl group, butyl, isopropyl, substitution or unsubstituted
Phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substitution or unsubstituted
Fluorenyl, substituted or unsubstituted triphenylene, two fluorenyl of substituted or unsubstituted spiral shell, substituted or unsubstituted pyrenyl, substitution
Or unsubstituted indenyl, substituted or unsubstituted base, substituted or unsubstituted carbazyl, substituted or unsubstituted pyridine radicals,
It is substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted indyl, substituted or unsubstituted furyl, substituted or unsubstituted
Thienyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted quinoline
One kind in quinoline base.
Preferably, the one kind of organic luminescent compounds of the invention in chemical constitution as follows：
Present invention also offers a kind of organic electroluminescence device, the organic electroluminescence device include cathode, anode with
And one or more organic matter layers, between cathode and anode, at least one layer in organic matter layer contains above-mentioned organic matter layer
The organic luminescent compounds of the present invention.
Further, organic matter layer includes electron transfer layer, and electron transfer layer includes the organic light emission of the invention described above
Compound.
Beneficial effect：Compared with prior art, it is an advantage of the invention that the organic luminescent compounds of the present invention are with big
The aromatic series organic molecule of plane, its conjugated system is larger, therefore has higher electron mobility, and in addition the present invention's is organic
Luminophor also has preferable heat endurance and dissolubility, is conducive to material filming；Using the organic light emission of the present invention
Organic electroluminescence device of the compound as organic matter layer, has relatively low driving voltage, higher luminous efficiency, and has
Longer service life.
Embodiment
With reference to specific embodiment, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention, after the present invention has been read, various equivalences of the those skilled in the art to the present invention
The modification of form falls within the application appended claims limited range.
A kind of organic luminescent compounds, the compound have the general structure as shown in structural formula I：
Wherein, R1、R2、R3、R4The independent alkyl selected from substituted or unsubstituted C1~C60, substituted or unsubstituted C6
The aryl of~C60, substituted or unsubstituted C3~C60 heteroaryl in one kind.
Preferably, R1、R2、R3、R4It is the independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted
The aryl of C6~C30, substituted or unsubstituted C3~C30 heteroaryl in one kind.
Most preferably, R1、R2、R3、R4Independent is selected from methyl, ethyl, propyl group, butyl, isopropyl, substitution or unsubstituted
Phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substitution or unsubstituted
Fluorenyl, substituted or unsubstituted triphenylene, two fluorenyl of substituted or unsubstituted spiral shell, substituted or unsubstituted pyrenyl, substitution
Or unsubstituted indenyl, substituted or unsubstituted base, substituted or unsubstituted carbazyl, substituted or unsubstituted pyridine radicals,
It is substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted indyl, substituted or unsubstituted furyl, substituted or unsubstituted
Thienyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted quinoline
One kind in quinoline base.
According to the present invention, above-mentioned R1、R2、R3、R4On substituent independence selected from cyano group, halogen, trifluoromethyl, nitro,
The alkoxy of C1~C10, the alkyl of C1~C10, the cycloalkyl of C3~C20, the aryl of C6~C24, C6~C24 aryloxy group,
The arylthio of C6~C24, the heteroaryl of C6~C24, C3~C20 heterocyclic radical in one kind.
Alkyl of the present invention refers to minus the alkyl that a hydrogen atom forms in alkane molecule, it can be straight chain alkane
Base, branched alkyl, cycloalkyl, example may include methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl group, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Aryl of the present invention refers to after a hydrogen atom is minused on the aromatic core carbon of aromatic hydrocarbon molecule, is left the total of univalent perssad
Claiming, it can be monocyclic aryl or fused ring aryl, and example may include phenyl, xenyl, naphthyl, anthryl, phenanthryl or pyrenyl etc., but
Not limited to this.
Heteroaryl of the present invention refers to the group that one or more of aryl aromatic core carbon is substituted by hetero atom
General name, the hetero atom include but not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl
Base, example may include pyridine radicals, pyrrole radicals, pyridine radicals, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene
Fen base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
Preferably, the one kind of organic luminescent compounds of the invention in chemical constitution as follows：
The synthetic method of the organic luminescent compounds of the present invention is as follows：
(1) in the four-hole boiling flask equipped with thermometer, blender, water knockout drum and condenser pipe, compound A-1 is added
(47mmol), compound A-2 (45mmol), ethylene glycol ethyl ether (250ml) and pyridine (0.2g), stirring are warming up to 140 DEG C, insulation
React 3 it is small when, reaction solution stirring is cooled to 40 DEG C, filtering, filter cake is washed with ethanol, is washed with water, dry, obtains compound
A。
(2) under nitrogen protection, compound A and dry THF are added into flask, reaction system is cooled to -40 DEG C,
The THF solution of the compound a-a just prepared is slowly added dropwise again, after being added dropwise to complete, reaction system is continued stirring 2 at room temperature
Hour.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted with ether, the anhydrous MgSO of organic phase4It is dry,
Decompression boils off solvent, and crude product is carried out column chromatography, obtains compound I-a；
Under nitrogen protection, compound I-a and dry THF are added into flask, reaction system is cooled to -40 DEG C,
The THF solution of the compound a-b just prepared is slowly added dropwise again, after being added dropwise to complete, reaction system is continued stirring 2 at room temperature
Hour.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted with ether, the anhydrous MgSO of organic phase4It is dry,
Decompression boils off solvent, and crude product is carried out column chromatography, obtains compound I.
(3) under nitrogen protection, into flask, obtained solid and toluene above is added, is heated to reflux, is leaked by constant pressure addition
Bucket is slowly added to chloroacetic chloride, and after being added dropwise to complete, continuation is stirred under reflux conditions, until all raw materials and intermediate convert completely
Into product.After question response system is cooled to room temperature, reaction solution, which is slowly poured into petroleum ether, separates out product, stands a few hours
Afterwards, filter, crude product obtains compound II with petroleum ether/re crystallization from toluene.
(4) under nitrogen protection, compound II and dry THF are added into flask, is added by constant pressure funnel
The THF solution of the compound b-a prepared in advance, after being added dropwise to complete, reaction mixture be stirred at room temperature 2 it is small when, Ran Houzai
Flow back 2 it is small when, collect the solid of generation, compound II-b arrived through column chromatography purifies and separates；
Under nitrogen protection, compound II-b and dry THF are added into flask, thing is added by constant pressure funnel
The THF solution of the compound b-b first prepared, after being added dropwise to complete, reaction mixture be stirred at room temperature 2 it is small when, then return again
Flow 2 it is small when, collect the solid of generation, through column chromatography purifies and separates to the compound shown in structural formula I.
The synthetic route of the organic luminescent compounds of the present invention is not particularly limited, those skilled in the art can be used
Known popular response.
Present invention also offers a kind of organic electroluminescence device, the organic electroluminescence device include cathode, anode with
And one or more organic matter layers, between cathode and anode, at least one layer in organic matter layer contains above-mentioned organic matter layer
The organic luminescent compounds of the present invention.In cathode portion, in order to increase the luminous efficiency of device, it usually needs low work function
The metals such as Ag, Al, Ca, In, Li, Mg, or the composition metal such as Mg-Ag, Li-Al of low work function make cathode.In anode
In the selection of material, material should have high work function and light-transmissive, such as tin indium oxide (ITO), the indium oxide heart in itself
(IZO), stannic oxide (SnO2), zinc oxide (ZnO) etc..
The organic matter layer of the organic electroluminescence device of the present invention has single layer structure, or optionally has wherein two
The sandwich construction of a or more organic matter layer layering.The organic electroluminescence device of the present invention can have hole injection layer, sky
Cave transport layer, luminous material layer, electron transfer layer, electron injecting layer or the cushion work being placed between anode and hole injection layer
For organic matter layer.However, the structure not limited to this of organic electroluminescence device, but may include small number of organic matter layer.
The thickness of the organic matter layer of organic luminescent compounds containing the present invention is not higher than 6 μm, is preferably not higher than 0.3 μm, and more excellent
Elect 0.002~0.3 μm as.If desired, the organic matter layer of the organic luminescent compounds containing the present invention can further include this
The known other materials that can carry out hole injection, hole transport, luminous, electric transmission and electron injection in field.
The organic electroluminescence device of the present invention can be prepared by known methods using known materials, only can be at one layer
Or the organic luminescent compounds of the present invention are included in multilayer organic matter layer.
The organic luminescent compounds of the present invention specifically can be as the electron transfer layer for preparing organic electroluminescence device.Adopt
Organic electroluminescence device is preferably：The ITO on transparent glass is attached to as anode, hole injection layer, hole transport
Layer, luminous material layer, organic luminescent compounds of the invention are as electron transfer layer, electron injecting layer, metallic cathode.
The organic electroluminescence device of the present invention can be widely applied to FPD, solid state lighting, Organophotoreceptor or have
The fields such as machine thin film transistor (TFT).
The present invention has no particular limits the raw material employed in following embodiments, can be for commercial product or using this
Preparation method known to field technology personnel is prepared.
Embodiment 1：
The preparation of compound II-1
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -1 just prepared is slowly added dropwise by reaction system
The THF solution of (45.3g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (52.0g, 75%) of the cis-trans isomerism of thing I-1.
Under nitrogen protection, into 250ml flasks, obtained solid (34.6g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-1 (25.5g, 70%).Mass spectrum m/z：Theoretical value：729.66；Measured value：731.74.Theoretical elemental content (%)
C48H26Cl2N4：C,79.01；H,3.59；Cl,9.72；N,7.68；Survey constituent content (%)：C,78.95；H,3.68；Cl,
9.70；N,7.67.The above results confirm that it is target product to obtain product.
The preparation of compound TM1
Under nitrogen protection, compound II-1 (18.2g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-1 (5.0g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM1 (14.0g, 69%).Mass spectrum m/z：Theoretical value：812.98；Measured value：814.77.Theoretical elemental
Content (%) C60H36N4：C,88.64；H,4.46；N,6.89；Survey constituent content (%)：C,88.61；H,4.51；N,6.85.
The above results confirm that it is target product to obtain product.
Embodiment 2：
The preparation of compound II-2
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -2 just prepared is slowly added dropwise by reaction system
The THF solution of (45.3g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (50.6g, 73%) of the cis-trans isomerism of thing I-2.
Under nitrogen protection, into 250ml flasks, obtained solid (34.6g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-2 (24.1g, 66%).Mass spectrum m/z：Theoretical value：729.66；Measured value：731.85.Theoretical elemental content (%)
C48H26Cl2N4：C,79.01；H,3.59；Cl,9.72；N,7.68；Survey constituent content (%)：C,78.94；H,3.70；Cl,
9.69；N,7.67.The above results confirm that it is target product to obtain product.
The preparation of compound TM2
Under nitrogen protection, compound II-2 (18.2g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-2 (9.6g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM2 (15.4g, 64%).Mass spectrum m/z：Theoretical value：965.17；Measured value：967.45.Theoretical elemental
Content (%) C72H44N4：C,89.60；H,4.60；N,5.80；Survey constituent content (%)：C,89.58；H,4.65；N,5.77.
The above results confirm that it is target product to obtain product.
Embodiment 3：
The preparation of compound II-3
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -3 just prepared is slowly added dropwise by reaction system
The THF solution of (51.6g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (56.4g, 76%) of the cis-trans isomerism of thing I-3.
Under nitrogen protection, into 250ml flasks, obtained solid (37.1g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-3 (28.1g, 72%).Mass spectrum m/z：Theoretical value：779.68；Measured value：781.89.Theoretical elemental content (%)
C50H24Cl2N6：C,77.02；H,3.10；Cl,9.09；N,10.78；Survey constituent content (%)：C,77.01；H,3.17；Cl,
9.06；N,10.75.The above results confirm that it is target product to obtain product.
The preparation of compound TM3
Under nitrogen protection, compound II-3 (19.5g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-3 (6.5g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM3 (16.0g, 70%).Mass spectrum m/z：Theoretical value：913.02；Measured value：915.14.Theoretical elemental
Content (%) C64H32N8：C,84.19；H,3.53；N,12.27；Survey constituent content (%)：C,84.16；H,3.59；N,
12.24.The above results confirm that it is target product to obtain product.
Embodiment 4：
The preparation of compound II-12
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -12 just prepared is slowly added dropwise by reaction system
The THF solution of (45.6g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (51.4g, 74%) of the cis-trans isomerism of thing I-12.
Under nitrogen protection, into 250ml flasks, obtained solid (34.7g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-12 (25.2g, 69%).Mass spectrum m/z：Theoretical value：731.64；Measured value：733.81.Theoretical elemental content (%)
C46H24Cl2N6：C,75.52；H,3.31；Cl,9.69；N,11.49；Survey constituent content (%)：C,75.49；H,3.39；Cl,
9.67；N,11.46.The above results confirm that it is target product to obtain product.
The preparation of compound TM12
Under nitrogen protection, compound II-12 (18.3g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-12 (5.1g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM12 (13.7g, 67%).Mass spectrum m/z：Theoretical value：816.93；Measured value：818.62.Theoretical elemental
Content (%) C56H32N8：C,82.33；H,3.95；N,13.72；Survey constituent content (%)：C,82.31；H,4.03；N,
13.66.The above results confirm that it is target product to obtain product.
Embodiment 5：
The preparation of compound II-24
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -24 just prepared is slowly added dropwise by reaction system
The THF solution of (58.1g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (50.9g, 64%) of the cis-trans isomerism of thing I-24.
Under nitrogen protection, into 250ml flasks, obtained solid (39.7g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-24 (25.0g, 60%).Mass spectrum m/z：Theoretical value：831.76；Measured value：833.62.Theoretical elemental content (%)
C54H28Cl2N6：C,77.98；H,3.39；Cl,8.52；N,10.10；Survey constituent content (%)：C,77.94；H,3.47；Cl,
8.51；N,10.07.The above results confirm that it is target product to obtain product.
The preparation of compound TM24
Under nitrogen protection, compound II-24 (20.8g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-24 (5.0g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM24 (13.5g, 59%).Mass spectrum m/z：Theoretical value：915.07；Measured value：917.66.Theoretical elemental
Content (%) C66H38N6：C,86.63；H,4.19；N,9.18；Survey constituent content (%)：C,86.61；H,4.24；N,9.15.
The above results confirm that it is target product to obtain product.
Embodiment 6：
The preparation of compound II-27
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -27 just prepared is slowly added dropwise by reaction system
The THF solution of (61.8g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (59.4g, 72%) of the cis-trans isomerism of thing I-27.
Under nitrogen protection, into 250ml flasks, obtained solid (41.2g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-27 (28.0g, 65%).Mass spectrum m/z：Theoretical value：861.78；Measured value：863.94.Theoretical elemental content (%)
C56H30Cl2N4O2：C,78.05；H,3.51；Cl,8.23；N,6.50；O,3.71；Survey constituent content (%)：C,78.02；H,
3.59；Cl,8.21；N,6.48；O,3.69.The above results confirm that it is target product to obtain product.
The preparation of compound TM27
Under nitrogen protection, compound II-27 (21.5g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-27 (5.0g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM27 (15.1g, 64%).Mass spectrum m/z：Theoretical value：945.09；Measured value：947.24.Theoretical elemental
Content (%) C68H40N4O2：C,86.42；H,4.27；N,5.93；O,3.39；Survey constituent content (%)：C,86.40；H,
4.34；N,5.91；O,3.36.The above results confirm that it is target product to obtain product.
Embodiment 7：
The preparation of compound II-32
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -32 just prepared is slowly added dropwise by reaction system
The THF solution of (74.4g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (62.9g, 68%) of the cis-trans isomerism of thing I-32.
Under nitrogen protection, into 250ml flasks, obtained solid (46.2g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-32 (31.7g, 66%).Mass spectrum m/z：Theoretical value：961.99；Measured value：963.76.Theoretical elemental content (%)
C66H42Cl2N4：C,82.40；H,4.40；Cl,7.37；N,5.82；Survey constituent content (%)：C,82.38；H,4.45；Cl,
7.35；N,5.81.The above results confirm that it is target product to obtain product.
The preparation of compound TM32
Under nitrogen protection, compound II-32 (24.0g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-32 (3.0g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM32 (15.9g, 65%).Mass spectrum m/z：Theoretical value：977.27；Measured value：979.32.Theoretical elemental
Content (%) C72H56N4：C,88.49；H,5.78；N,5.73；Survey constituent content (%)：C,88.46；H,5.83；N,5.71.
The above results confirm that it is target product to obtain product.
Embodiment 8：
The preparation of compound II-53
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -53 just prepared is slowly added dropwise by reaction system
The THF solution of (46.8g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (50.0g, 71%) of the cis-trans isomerism of thing I-53.
Under nitrogen protection, into 250ml flasks, obtained solid (35.2g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-53 (24.8g, 67%).Mass spectrum m/z：Theoretical value：741.71；Measured value：743.83.Theoretical elemental content (%)
C44H22Cl2N4S2：C,71.25；H,2.99；Cl,9.56；N,7.55；S,8.64；Survey constituent content (%)：C,71.23；H,
3.05；Cl,9.54；N,7.54；S,8.63.The above results confirm that it is target product to obtain product.
The preparation of compound TM53
Under nitrogen protection, compound II-53 (18.5g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-53 (5.4g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM53 (13.4g, 64%).Mass spectrum m/z：Theoretical value：837.06；Measured value：839.52.Theoretical elemental
Content (%) C52H28N4S4：C,74.61；H,3.37；N,6.69；S,15.32；Survey constituent content (%)：C,74.59；H,
3.41；N,6.68；S,15.30.The above results confirm that it is target product to obtain product.
Embodiment 9：
The preparation of compound II-59
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -59 just prepared is slowly added dropwise by reaction system
The THF solution of (64.8g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (62.0g, 73%) of the cis-trans isomerism of thing I-59.
Under nitrogen protection, into 250ml flasks, obtained solid (42.4g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-59 (29.7g, 67%).Mass spectrum m/z：Theoretical value：885.81；Measured value：887.93.Theoretical elemental content (%)
C56H30Cl2N8：C,75.93；H,3.41；Cl,8.00；N,12.65；Survey constituent content (%)：C,75.89；H,3.47；Cl,
8.01；N,12.62.The above results confirm that it is target product to obtain product.
The preparation of compound TM59
Under nitrogen protection, compound II-59 (22.1g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-59 (5.0g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM59 (16.0g, 66%).Mass spectrum m/z：Theoretical value：969.12；Measured value：971.58.Theoretical elemental
Content (%) C68H40N8：C,84.28；H,4.16；N,11.56；Survey constituent content (%)：C,84.26；H,4.21；N,
11.53.The above results confirm that it is target product to obtain product.
Embodiment 10：
The preparation of compound II-62
Under nitrogen protection, into 500ml flasks add compound A (53.6g, 100mmol) and through Na/ benzophenone at
The THF (200ml) for the drying managed, is cooled to -40 DEG C, then the compound a -62 just prepared is slowly added dropwise by reaction system
The THF solution of (33.3g, 250mmol), after being added dropwise to complete, room temperature is slowly raised to by reaction system, and continues to stir at room temperature
2 hours.Reaction solution is slowly poured into saturated ammonium chloride solution, product is extracted three times with ether (200ml), is merged organic
Phase, and by obtained organic phase with anhydrous MgSO4Dry, decompression boils off solvent, and crude product is carried out column chromatography, must contain chemical combination
The solid mixture (41.2g, 69%) of the cis-trans isomerism of thing I-59.
Under nitrogen protection, into 250ml flasks, obtained solid (29.8g, 50mmol) and toluene (100ml) above are added,
It is heated to reflux, chloroacetic chloride (25ml) is slowly added to by constant pressure funnel, after being added dropwise to complete, continuation is stirred under reflux conditions
Mix, until all raw materials and intermediate are fully converted into product.After question response system is cooled to room temperature, reaction solution is slowly poured into
Product is separated out into petroleum ether (400ml), after standing a few hours, filtering, crude product is with petroleum ether/re crystallization from toluene
Compound II-62 (20.6g, 65%).Mass spectrum m/z：Theoretical value：633.58；Measured value：635.69.Theoretical elemental content (%)
C40H26Cl2N4：C,75.83；H,4.14；Cl,11.19；N,8.84；Survey constituent content (%)：C,75.80；H,4.20；Cl,
11.17；N,8.83.The above results confirm that it is target product to obtain product.
The preparation of compound TM62
Under nitrogen protection, compound II-62 (15.8g, 25mmol) and dry THF are added into 250ml flasks
(100ml), the THF solution of the compound b-62 (2.2g, 60mmol) prepared in advance is added by constant pressure funnel, is added dropwise
After the completion of, reaction mixture be stirred at room temperature 2 it is small when, then flow back again 2 it is small when, collect the solid of generation, it is pure through column chromatography
Change and separated arrive compound TM62 (10.1g, 65%).Mass spectrum m/z：Theoretical value：620.80；Measured value：622.95.Theoretical elemental
Content (%) C44H36N4：C,85.13；H,5.85；N,9.03；Survey constituent content (%)：C,85.12；H,5.88；N,9.01.
The above results confirm that it is target product to obtain product.
Other target products are synthesized with reference to the synthetic method of above-described embodiment 1-10.
Application Example 1：The preparation of luminescent device 1
Ito glass substrate is placed in distilled water and is cleaned 2 times, ultrasonic washing 15 minutes is different after distilled water cleans
Ultrasonic washing is later dry in order for propyl alcohol, acetone, methanol equal solvent, is transferred in plasma washing machine, by above-mentioned base
Plate washs 5 minutes, is sent in evaporator.
Vacuum evaporation HAT-CN is as hole transmission layer, evaporation thickness 10nm on above-mentioned ito anode substrate.In hole
Vacuum evaporation CBP is as luminescent material layer main body, 5% Ir (ppy) in transport layer3Adulterated as green light phosphorescence, evaporation thickness
For 30nm.The compound TM1 of the vacuum evaporation present invention is as electron transfer layer, evaporation thickness 50nm on luminous material layer.
Vacuum evaporation Al is as cathode, evaporation thickness 150nm on the electron transport layer.
Application Example 2：The preparation of luminescent device 2
Change the compound TM1 in Application Example 1 into compound TM2.
Application Example 3：The preparation of luminescent device 3
Change the compound TM1 in Application Example 1 into compound TM3.
Application Example 4：The preparation of luminescent device 4
Change the compound TM1 in Application Example 1 into compound TM12.
Application Example 5：The preparation of luminescent device 5
Change the compound TM1 in Application Example 1 into compound TM24.
Application Example 6：The preparation of luminescent device 6
Change the compound TM1 in Application Example 1 into compound TM27.
Application Example 7：The preparation of luminescent device 7
Change the compound TM1 in Application Example 1 into compound TM32.
Application Example 8：The preparation of luminescent device 8
Change the compound TM1 in Application Example 1 into compound TM53.
Application Example 9：The preparation of luminescent device 9
Change the compound TM1 in Application Example 1 into compound TM59.
Application Example 10：The preparation of luminescent device 10
Change the compound TM1 in Application Example 1 into compound TM62.
Comparative example 1
Ito glass substrate is placed in distilled water and is cleaned 2 times, ultrasonic washing 15 minutes is different after distilled water cleans
Ultrasonic washing is later dry in order for propyl alcohol, acetone, methanol equal solvent, is transferred in plasma washing machine, by above-mentioned base
Plate washs 5 minutes, is sent in evaporator.
Vacuum evaporation HAT-CN is as hole transmission layer, evaporation thickness 10nm on above-mentioned ito anode substrate.In hole
Vacuum evaporation CBP is as luminescent material layer main body, 5% Ir (ppy) in transport layer3Adulterated as green light phosphorescence, evaporation thickness
For 30nm.Vacuum evaporation TPBI is as electron transfer layer, evaporation thickness 50nm on luminous material layer.On the electron transport layer
Vacuum evaporation Al is as cathode, evaporation thickness 150nm.
The characteristics of luminescence test result of luminescent device prepared by Application Example 1-10 of the present invention and comparative example 1
As shown in table 2.
Table 2
From Table 2, it can be seen that the organic luminescent compounds of the present invention are applied to organic electroluminescence as electron transport material
In luminescent device, which shows relatively low driving voltage, higher luminous efficiency and longer use
Service life, and there is preferable durability and reliability.
Claims (6)
1. a kind of organic luminescent compounds, it is characterised in that the compound has the general structure as shown in structural formula I：
Wherein, R1、R2、R3、R4The independent alkyl selected from substituted or unsubstituted C1~C60, substituted or unsubstituted C6~C60
Aryl, substituted or unsubstituted C3~C60 heteroaryl in one kind.
A kind of 2. organic luminescent compounds according to claim 1, it is characterised in that the R1、R2、R3、R4Independent choosing
The aryl of alkyl, substituted or unsubstituted C6~C30 from substituted or unsubstituted C1~C30, substituted or unsubstituted C3~
One kind in the heteroaryl of C30.
A kind of 3. organic luminescent compounds according to claim 1, it is characterised in that the R1、R2、R3、R4Independent choosing
Do not take from methyl, ethyl, propyl group, butyl, isopropyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substitution or
The anthryl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substitution or
Unsubstituted two fluorenyl of spiral shell, substituted or unsubstituted pyrenyl, substituted or unsubstituted indenyl, substituted or unsubstituted base, take
Generation or unsubstituted carbazyl, substituted or unsubstituted pyridine radicals, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted Yin
Diindyl base, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted dibenzothiophene, take
One kind in generation or unsubstituted dibenzofuran group, substituted or unsubstituted quinolyl.
4. a kind of organic luminescent compounds according to claim 1, it is characterised in that the organic luminescent compounds are selected from
One kind in chemical constitution as follows：
5. a kind of organic electroluminescence device, it is characterised in that the organic electroluminescence device includes cathode, anode and one
A or multiple organic matter layers, between cathode and anode, at least one layer in the organic matter layer contains the organic matter layer
Organic luminescent compounds described in claim 1-4 any one.
6. a kind of organic electroluminescence device according to claim 5, it is characterised in that the organic matter layer includes electronics
Transport layer, the electron transfer layer include the organic luminescent compounds described in claim 1-4 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711122682.3A CN107936951A (en) | 2017-11-14 | 2017-11-14 | A kind of organic luminescent compounds and its organic electroluminescence device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711122682.3A CN107936951A (en) | 2017-11-14 | 2017-11-14 | A kind of organic luminescent compounds and its organic electroluminescence device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107936951A true CN107936951A (en) | 2018-04-20 |
Family
ID=61934075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711122682.3A Withdrawn CN107936951A (en) | 2017-11-14 | 2017-11-14 | A kind of organic luminescent compounds and its organic electroluminescence device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107936951A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3924430A4 (en) * | 2019-02-14 | 2023-04-19 | Lleaf Pty Ltd | Photoperiodic control of phytochrome with materials |
-
2017
- 2017-11-14 CN CN201711122682.3A patent/CN107936951A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3924430A4 (en) * | 2019-02-14 | 2023-04-19 | Lleaf Pty Ltd | Photoperiodic control of phytochrome with materials |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106661038B (en) | Organic compound, organic photoelectric device and display device | |
| CN107652189A (en) | A kind of fluorene kind derivative and its organic luminescent device | |
| CN108658837A (en) | A kind of organic electroluminescence device | |
| CN113636944B (en) | Organic compound, electronic element comprising same and electronic device | |
| CN109467511A (en) | A kind of aromatic amine compounds and its organic luminescent device | |
| CN109134348A (en) | A kind of carbazole compound and its organic luminescent device | |
| CN109293516A (en) | A kind of tri-arylamine group compound and its organic luminescent device | |
| WO2022160928A1 (en) | Nitrogen-containing compound, and electronic component and electronic device containing same | |
| CN113105420A (en) | Fused ring arylamine compound, application thereof and organic electroluminescent device containing compound | |
| CN110818675A (en) | Organic compound and application thereof | |
| CN108929234A (en) | A kind of preparation of aromatic amine derivatives and its organic electroluminescence device | |
| CN109020903A (en) | A kind of triarylamine derivative and its organic electroluminescence device | |
| CN114805179B (en) | Nitrogen-containing compound, organic electroluminescent device and electronic device | |
| CN109360905A (en) | A kind of organic electroluminescence device | |
| CN103183664B (en) | Naphthacridine derivate, preparation method and application thereof, and organic light-emitting device | |
| WO2022242521A1 (en) | Condensed azacyclic compound, use thereof, and organic electroluminescent device comprising condensed azacyclic compound | |
| CN109192857A (en) | A kind of organic electroluminescence device | |
| CN109053632A (en) | A kind of fluorene kind derivative and its organic electroluminescence device | |
| CN107915745A (en) | A kind of derivative and its organic luminescent device containing phenanthro- glyoxaline structure | |
| CN109400487A (en) | A kind of fluorene kind derivative and its organic electroluminescence device | |
| CN109134369A (en) | A kind of Acridine derivatives and its organic luminescent device | |
| CN109096277A (en) | A kind of derivative of phenanthroline and its organic electroluminescence device | |
| CN109020901A (en) | A kind of preparation of aromatic amine derivatives and its organic electroluminescence device | |
| CN110759936B (en) | Compound, display panel and display device | |
| CN115109051B (en) | Aromatic amine compound, organic electroluminescent device and electronic device |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180420 |
|
| WW01 | Invention patent application withdrawn after publication |