CN110494430A - New compound and the organic illuminating element for utilizing it - Google Patents
New compound and the organic illuminating element for utilizing it Download PDFInfo
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- H—ELECTRICITY
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- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
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- 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
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- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
Abstract
The present invention provides new compound and the organic illuminating element using it.
Description
Technical field
With the mutual reference of related application
This application claims the South Korea patent applications the 10-2017-0135923rd and 2018 based on October 19th, 2017
South Korea patent application the 10-2018-0062161st priority on May 30, in the document comprising the South Korea patent application
Entire disclosure as part of this specification.
The present invention relates to novel amine compound and include its organic illuminating element.
Background technique
Under normal conditions, organic light emission phenomenon refers to the phenomenon that converting electrical energy into luminous energy using organic substance.Using having
The organic illuminating element of machine luminescence phenomenon have wide viewing angle, excellent contrast, fast response time, brightness, driving voltage and
Response speed excellent, therefore largely studied.
Organic illuminating element usually has the organic matter comprising anode and cathode and between above-mentioned anode and cathode
The structure of layer.In order to improve the efficiency and stability of organic illuminating element, above-mentioned organic matter layer is in most cases by being utilized respectively
The multilayered structure that different substances is constituted is formed, for example, can be by hole injection layer, hole transmission layer, luminescent layer, electron-transport
The formation such as layer, electron injecting layer.For the structure of such organic illuminating element, if applying electricity between electrodes
Pressure, then hole is injected into organic matter layer from anode, and electronics is injected into organic matter layer from cathode, when institute's injected holes and electronics phase
It will form exciton (exciton) when chance, and light will be issued when the exciton transits to ground state again.
It is lasting to require to develop new material to the organic matter for organic illuminating element as described above.
Existing technical literature
Patent document
(patent document 0001) Korean Patent Publication No. the 10-2000-0051826th
Summary of the invention
Project to be solved
The present invention relates to novel amine compound and include its organic illuminating element.
The solution of project
The present invention
The present invention provides the compound indicated by following chemical formula 1:
[chemical formula 1]
In above-mentioned chemical formula 1,
X1To X4In, X1And X2、X2And X3Or X3And X4It being connect respectively with the * of following chemical formula 2, remaining is hydrogen,
[chemical formula 2]
A, the integer that c, d and e are 0 to 3,
The integer that b is 0 to 2,
X is 1 or 2,
R1To R5It is each independently hydrogen, deuterium, halogen group, cyano, substituted or unsubstituted C1-60Alkyl, substitution or not
Substituted C1-60Alkoxy, substituted or unsubstituted C1-60Alkylthio, substituted or unsubstituted C3-60Naphthenic base, substitution or not
Substituted C6-60Aryl or three (C1-60Alkyl) silicyl,
R indicates by following chemical formula 3 each independently,
[chemical formula 3]
In above-mentioned chemical formula 3,
L1、L2And L3It is each independently singly-bound；Substituted or unsubstituted C6-60Arlydene；Or it is substituted or unsubstituted
Comprising in N, O and S any one or more person heteroatomic C2-60Inferior heteroaryl,
Ar1And Ar2It is each independently substituted or unsubstituted C6-60Aryl；Or it is substituted or unsubstituted comprising being selected from
N, the heteroatomic C of any one in O and S or more person2-60Heteroaryl.
In addition, the present invention a kind of organic illuminating element is provided comprising: it is first electrode, opposed with above-mentioned first electrode
And the second electrode that has and has one layer or more of organic matter between above-mentioned first electrode and above-mentioned second electrode
Layer, one layer or more the compound comprising being indicated by above-mentioned chemical formula 1 in above-mentioned organic matter layer.
Invention effect
The material that may be used as the organic matter layer of organic illuminating element by the compound that above-mentioned chemical formula 1 indicates, organic
It can be realized the raising of efficiency, the raising of low driving voltage and/or life characteristic in light-emitting component.In particular, by above-mentioned chemistry
The compound that formula 1 indicates can be used as hole injection, hole transport, hole injection and transmission, luminous, electron-transport or electronics note
Enter material.
Detailed description of the invention
Fig. 1 illustrates the examples for the organic illuminating element being made of substrate 1, anode 2, luminescent layer 3, cathode 4.
Fig. 2 illustrate by substrate 1, anode 2, hole injection layer 5, hole transmission layer 6, luminescent layer 7, electron transfer layer 8, with
And the example of the organic illuminating element of the composition of cathode 4.
Specific embodiment
In the following, being illustrated in more details to help to understand the present invention.
The present invention provides the compound indicated by above-mentioned chemical formula 1.
In this specification,OrIndicate the key connecting with other substituent groups.
In this specification, " substituted or unsubstituted " this term refers to by selected from deuterium；Halogen group；Itrile group；Nitro；Hydroxyl
Base；Carbonyl；Ester group；Imide；Amino；Aoxidize phosphino-；Alkoxy；Aryloxy group；Alkyl sulfenyl (
Alkyl thioxy)；Artyl sulfo ( Aryl thioxy)；Alkyl sulphonyl (Alkyl sulfoxy)；Aryl sulfonyl (Aryl sulfoxy)；First silicon
Alkyl；Boryl；Alkyl；Naphthenic base；Alkenyl；Aryl；Aralkyl；Arylalkenyl；Alkylaryl；Alkyl amine group；Aralkyl amido；It is miscellaneous
Arylamine group；Arylamine group；Aryl phosphino-；Or include more than one in the more than one heterocycle in N, O and S atom
Substituent group substitution substituted or unsubstituted, or being formed by connecting by 2 or more substituent groups in foregoing illustrative substituent group
Base is substituted or unsubstituted.For example, " substituent group that 2 or more substituent groups are formed by connecting " can be xenyl.That is, xenyl can
Think aryl, can also be interpreted the substituent group that 2 phenyl are formed by connecting.
In this specification, the carbon atom number of carbonyl is not particularly limited, but preferably carbon atom number is 1 to 40.Specifically,
It can be the compound of following structure, but not limited to this.
In this specification, in ester group, the oxygen of ester group can by the straight chain of carbon atom number 1 to 25, branch or cyclic alkyl or
The aryl of carbon atom number 6 to 25 replaces.Specifically, can be the compound of following structural formula, but not limited to this.
In this specification, the carbon atom number of imide is not particularly limited, but preferably carbon atom number is 1 to 25.Specifically
For, it can be the compound of following structure, but not limited to this.
In this specification, silicyl specifically has trimethyl silyl, triethylsilyl, tertbutyldimethylsilyl chloride
Silylation, vinyldimethylsilyl, propyl-dimethyl silicyl, triphenyl-silyl, diphenylsilyl group,
Phenyl silyl groups etc., but not limited to this.
In this specification, boryl specifically has trimethyl boryl, triethyl group boryl, fert-butyidimethylsilyl boryl, triphenyl borine
Base, phenyl boryl etc., but not limited to this.
In this specification, as the example of halogen group, there are fluorine, chlorine, bromine or iodine.
In this specification, abovementioned alkyl can be linear chain or branched chain, and carbon atom number is not particularly limited, but preferably 1 to
40.According to an embodiment, the carbon atom number of abovementioned alkyl is 1 to 20.According to another embodiment, the carbon atom of abovementioned alkyl
Number is 1 to 10.According to another embodiment, the carbon atom number of abovementioned alkyl is 1 to 6.As the specific example of alkyl, there is first
Base, ethyl, propyl, n-propyl, isopropyl, butyl, normal-butyl, isobutyl group, tert-butyl, sec-butyl, 1- methyl-butvl, 1- second
Base-butyl, amyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1- methyl amyl, 2- methyl amyl, 4-
Methyl -2- amyl, 3,3- dimethylbutyl, 2- ethyl-butyl, heptyl, n-heptyl, 1- methylhexyl, cyclopentyl-methyl, hexamethylene
Ylmethyl, octyl, n-octyl, t-octyl, 1- methylheptyl, 2- ethylhexyl, 2- propylpentyl, n-nonyl, 2,2- dimethyl
Heptyl, 1- Ethyl-propyl, 1,1- Dimethyl-propyl, isohesyl, 2- methyl amyl, 4- methylhexyl, 5- methylhexyl etc., but
It's not limited to that.
In this specification, above-mentioned alkenyl can be linear chain or branched chain, and carbon atom number is not particularly limited, but preferably 2 to
40.According to an embodiment, the carbon atom number of above-mentioned alkenyl is 2 to 20.According to another embodiment, the carbon atom of above-mentioned alkenyl
Number is 2 to 10.According to another embodiment, the carbon atom number of above-mentioned alkenyl is 2 to 6.As specific example, there are vinyl, 1-
Acrylic, isopropenyl, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl, 1- pentenyl, 2- pentenyl, 3- pentenyl, 3- methyl-
1- cyclobutenyl, 1,3- butadienyl, allyl, 1- phenylethylene -1- base, 2- phenylethylene -1- base, 2,2- diphenylethlene -
1- base, 2- phenyl -2- (naphthalene -1- base) ethylene -1- base, 2,2- bis- (hexichol -1- base) ethylene -1- base, Stilbene base, styryls etc.,
But not limited to this.
In this specification, naphthenic base is not particularly limited, but the naphthenic base that preferred carbon atom number is 3 to 60, real according to one
Mode is applied, the carbon atom number of above-mentioned naphthenic base is 3 to 30.According to another embodiment, the carbon atom number of above-mentioned naphthenic base be 3 to
20.According to another embodiment, the carbon atom number of above-mentioned naphthenic base is 3 to 6.Specifically, having cyclopropyl, cyclobutyl, ring penta
Base, 3- methylcyclopentyl, 2,3- dimethylcyclopentyl, cyclohexyl, 3- methylcyclohexyl, 4- methylcyclohexyl, 2,3- dimethyl
Cyclohexyl, 3,4,5- trimethylcyclohexyls, 4- tert-butylcyclohexyl, suberyl, cyclooctyl etc., but not limited to this.
In this specification, aryl is not particularly limited, but preferably carbon atom number is 6 to 60 aryl, can be monocycle virtue
Base or polyaromatic.According to an embodiment, the carbon atom number of above-mentioned aryl is 6 to 30.According to an embodiment, above-mentioned aryl
Carbon atom number be 6 to 20.It can be phenyl, xenyl, terphenyl etc. as monocyclic aryl, but simultaneously about above-mentioned aryl
It is not limited to this.As above-mentioned polyaromatic, can for naphthalene, anthryl, phenanthryl, pyrenyl, base,Base, fluorenyl etc., but simultaneously
It is not limited to this.
In this specification, fluorenyl can be substituted, and 2 substituent groups can be bonded to each other and form spiro structure.In above-mentioned fluorenes
In the substituted situation of base, Ke Yiwei
Deng.But simultaneously
It is not limited to this.
In this specification, heterocycle is comprising more than one in O, N, Si and S as heteroatomic heterocycle, carbon atom
Number is not particularly limited, but preferably carbon atom number is 2 to 60.As the example of heterocycle, have thienyl, furyl, pyrrole radicals,
Imidazole radicals, thiazolyl,Oxazolyl,Di azoly, triazolyl, pyridyl group, bipyridyl, pyrimidine radicals, triazine radical, acridinyl,
Pyridazinyl, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, phthalazinyl, Pyridopyrimidine base, pyrido-pyrazine base, pyrazine
And pyrazinyl, isoquinolyl, indyl, carbazyl, benzoOxazolyl, benzimidazolyl, benzothiazolyl, benzo carbazole base,
It is benzothienyl, dibenzothiophene, benzofuranyl, phenanthroline (phenanthroline), differentOxazolyl, thiadiazoles
Base, phenothiazinyl and dibenzofuran group etc., it is not limited to this.
In this specification, the example phase of aralkyl, arylalkenyl, alkylaryl, aryl and above-mentioned aryl in arylamine group
Together.In this specification, aralkyl, alkylaryl, the alkyl in alkyl amine group are identical as the example of abovementioned alkyl.This specification
In, the heteroaryl in heteroaryl amine can apply with respect to the explanation of above-mentioned heterocycle.In this specification, alkenyl in arylalkenyl with
The example of above-mentioned alkenyl is identical.In this specification, arlydene is that divalent group can be applicable in above-mentioned about aryl in addition to this
Explanation.In this specification, inferior heteroaryl is that divalent group can be applicable in the above-mentioned explanation about heterocycle in addition to this.This
In specification, hydrocarbon ring not instead of 1 valence group, 2 substituent groups are combined into, and in addition to this, can be applicable in above-mentioned about aryl
Or the explanation of naphthenic base.In this specification, heterocycle not instead of 1 valence group, 2 substituent groups are combined into, in addition to this, can be with
It is applicable in the above-mentioned explanation about heterocycle.
In above-mentioned chemical formula 1, according to the binding site of chemical formula 2, above-mentioned chemical formula 1 is respectively by following chemical formula 1-1,1-
2 or 1-3 is indicated.
[chemical formula 1-1]
[chemical formula 1-2]
[chemical formula 1-3]
Preferably, a, b, c, d and e are 0.Furthermore it is preferred that R1To R5For hydrogen.
Preferably, L1For singly-bound, phenylene, biphenyl diyl, terphenyl diyl, quaterphenyl diyl, naphthalene-diyl, anthracene diyl,
Luxuriant and rich with fragrance diyl, triphenylene diyl, pyrene diyl, dimethyl fluorene diyl, aminomethyl phenyl fluorenes diyl, diphenylfluorene diyl, dibenzofurans
Diyl, dibenzothiophenes diyl, carbazole diyl or 9- phenyl -9H- carbazole diyl.It is highly preferred that L1For singly-bound or phenylene.
Preferably, L2And L3It is each independently singly-bound, phenylene, biphenyl diyl, terphenyl diyl, quaterphenyl diyl, naphthalene
Diyl, anthracene diyl, luxuriant and rich with fragrance diyl, triphenylene diyl, pyrene diyl, dimethyl fluorene diyl, aminomethyl phenyl fluorenes diyl, diphenylfluorene two
Base, spiro fluorene diyl, dibenzofurans diyl, dibenzothiophenes diyl, carbazole diyl or 9- phenyl -9H- carbazole diyl.
Preferably, Ar1And Ar2It is each independently phenyl, xenyl, terphenyl, tetrad phenyl, naphthalene, phenanthryl, two
Methylfluorenyl, dibenzo fluorenyl, Spirofluorene-based, dibenzofuran group, dibenzothiophene, carbazyl or 9- phenyl -9H carbazole
Base.
The typical example of the compound indicated by above-mentioned chemical formula 1 is as follows:
In addition, in the present invention, it as an example, can be by as follows by the compound that above-mentioned chemical formula 1-1 is indicated
The manufacturing method for stating reaction equation 1 is manufactured, and can be applicable to remaining compound indicated by chemical formula 1-2 and 1-3.
[reaction equation 1]
Above-mentioned reaction equation 1 is amine substitution reaction, is made by the above-mentioned chemical formula 1-a compound indicated and by above-mentioned chemical formula
The compound reaction that 1-b is indicated, thus reaction of the manufacture by the above-mentioned chemical formula 1-1 compound indicated.Above-mentioned reaction preferably exists
Have and carry out under conditions of palladium catalyst and alkali, the reactive group for amine substitution reaction can be changed to as known in the art anti-
Answer group.Preferably, above-mentioned X is halogen group (more preferably bromine or chlorine).Above-mentioned manufacturing method can be in aftermentioned Production Example
In it is more specific.
In addition, the present invention provides the organic illuminating element of the compound comprising being indicated by above-mentioned chemical formula 1.As an example
Son, the present invention a kind of organic illuminating element is provided comprising: first electrode, it is opposed with above-mentioned first electrode and have
Two electrodes and have one layer or more of organic matter layer between above-mentioned first electrode and above-mentioned second electrode, it is above-mentioned organic
One layer or more the compound comprising being indicated by above-mentioned chemical formula 1 in nitride layer.
The organic matter layer of organic illuminating element of the invention can be formed by single layer structure, can also by be laminated with two layers with
On the multilayered structure of organic matter layer formed.For example, organic illuminating element of the invention can have comprising hole injection layer, sky
The structure as organic matter layer such as cave transport layer, luminescent layer, electron transfer layer, electron injecting layer.But organic illuminating element
It's not limited to that for structure, may include more a small number of organic layers.
In addition, above-mentioned organic matter layer may include hole injection layer, hole transmission layer or carry out hole injection and biography simultaneously
Defeated layer, above-mentioned hole injection layer, hole transmission layer or to carry out the layer of hole injection and transmission simultaneously include by above-mentioned chemical formula
1 compound indicated.
In addition, above-mentioned organic matter layer may include luminescent layer, above-mentioned luminescent layer includes the chemical combination indicated by above-mentioned chemical formula 1
Object.In particular, compound according to the present invention can be used as the dopant of luminescent layer and use.
In addition, above-mentioned organic matter layer may include electron transfer layer or electron injecting layer, above-mentioned electron transfer layer or electronics
Implanted layer includes the compound indicated by above-mentioned chemical formula 1.
In addition, above-mentioned electron transfer layer, electron injecting layer or carry out simultaneously electron-transport and electron injection layer include by
The compound that above-mentioned chemical formula 1 indicates.
In addition, above-mentioned organic matter layer includes luminescent layer and electron transfer layer, above-mentioned electron transfer layer be may include by above-mentioned
The compound that chemical formula 1 indicates.
In addition, organic illuminating element according to the present invention can be to be sequentially laminated with anode, one layer or more on substrate
The organic illuminating element of the structure (standard type (normal type)) of organic matter layer and cathode.In addition, according to the present invention organic
Light-emitting component (can be inverted for the reverse structure of the organic matter layer and anode that are sequentially laminated with cathode, one layer or more on substrate
Type (inverted type)) organic illuminating element.For example, the knot of the organic illuminating element of an embodiment according to the present invention
Structure is illustrated in Fig. 1 and 2.
Fig. 1 illustrates the examples for the organic illuminating element being made of substrate 1, anode 2, luminescent layer 3, cathode 4.In institute as above
In the structure stated, it may be embodied in above-mentioned luminescent layer by the compound that above-mentioned chemical formula 1 indicates.
Fig. 2 illustrate by substrate 1, anode 2, hole injection layer 5, hole transmission layer 6, luminescent layer 7, electron transfer layer 8 with
And the example of the organic illuminating element of the composition of cathode 4.In structure as described above, the compound that is indicated by above-mentioned chemical formula 1
It may be embodied in one layer or more in above-mentioned hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.
Organic illuminating element according to the present invention includes by above-mentioned chemical formula 1 in addition to one layer or more in above-mentioned organic matter layer
Other than the compound of expression, it can use material well known in the art and method manufactured.In addition, working as above-mentioned organic light emission
In the case that element includes multiple organic matter layers, above-mentioned organic matter layer can be formed by identical substance or different substances.
For example, organic illuminating element according to the present invention can be by stacking gradually first electrode, organic matter on substrate
Layer and second electrode and manufacture.At this moment it can manufacture as follows: utilize sputtering method (sputtering) or electron beam evaporation method (e-
Beam evaporation) etc PVD (physical Vapor Deposition, physical vapour deposition (PVD)) method, in substrate
Upper evaporation metal or conductive metal oxide or their alloy and form anode, then on the anode formed packet
Organic matter layer containing hole injection layer, hole transmission layer, luminescent layer and electron transfer layer, vapor deposition can on the organic matter layer later
Substance as cathode and manufacture.Other than this method, can also on substrate successively evaporation cathode substance, organic matter
Layer, anode material and manufacture organic illuminating element.
In addition, the compound indicated by above-mentioned chemical formula 1 not only can use vacuum steaming when manufacturing organic illuminating element
Plating method can also form organic matter layer using solution coating method.Herein, so-called solution coating method refers to, spin-coating method, dip-coating
Method, knife coating, ink jet printing method, silk screen print method, spray-on process, rolling method etc., it is not limited to this.
In addition to these methods, can also on substrate successively evaporation cathode substance, organic matter layer, anode material and make
Make organic illuminating element (WO2003/012890).But it's not limited to that for manufacturing method.
As an example, above-mentioned first electrode is anode, and above-mentioned second electrode is cathode or above-mentioned first electrode is
Cathode, above-mentioned second electrode are anode.
As above-mentioned anode material, generally for enabling hole successfully to inject to organic matter layer, preferably work function
Big substance.As the concrete example of above-mentioned anode material, there are the metals such as vanadium, chromium, copper, zinc, gold or their alloy；Zinc oxide,
The metal oxides such as indium oxide, tin indium oxide (ITO), indium zinc oxide (IZO)；Such as ZnO:Al or SNO2: the metals such as Sb and oxidation
The combination of object；Poly- (3 methyl thiophene), poly- [3,4- (ethylidene -1,2- dioxy) thiophene] (PEDOT), polypyrrole and polyaniline etc.
Electroconductive polymer etc., but it is not limited to this.
As above-mentioned cathode substance, generally for electronics is injected easily to organic matter layer, preferably work function is small
Substance.As the concrete example of above-mentioned cathode substance, there are the metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin and lead
Or their alloy；Such as LiF/Al or LiO2Multilayered structures substance such as/Al etc., it is not limited to this.
Above-mentioned hole injection layer is the layer in the hole that injection carrys out self-electrode, as hole injecting material, preferably followingization
Close object: the ability with transporting holes has hole injection effect from anode, for the excellent of luminescent layer or luminescent material
Hole inject effect, prevent in luminescent layer generated exciton to migrate to electron injecting layer or electron injection material, and thin
Film Forming ability is excellent.It is preferred that HOMO (highest occupied molecular orbital(HOMO), the highest occupied of hole injecting material
Molecular orbital) between the work function of anode material and the HOMO of surrounding organic matter layer.As hole infusion
The concrete example of matter has metalloporphyrin (porphyrin), Oligopoly thiophene, aryl amine system organic matter, six nitriles, six azepine benzophenanthrene system to have
It is organic matter, anthraquinone and polyaniline and polythiophene that machine object, quinacridone (quinacridone), which are organic matter, (perylene),
It is electroconductive polymer etc., it is not limited to this.
Above-mentioned hole transmission layer is to receive the hole from hole injection layer and by the layer of hole transport to luminescent layer, as
Hole transporting material is the substance that can be received the hole from anode or hole injection layer and transfer them to luminescent layer, right
The big substance of hole mobility is suitable.As concrete example, there are aryl amine system organic matter, electroconductive polymer and simultaneously
There are conjugate moieties and the block copolymer of non-conjugated portion etc., it is not limited to this.
It is that can receive respectively hole and electronics from hole transmission layer and electron transfer layer and make as above-mentioned luminescent substance
They in conjunction with and issue the substance of the light of visible light region, preferably for the high substance of the quantum efficiency of fluorescence or phosphorescence.As
Specific example has 8-hydroxyquinoline aluminum complex (Alq3)；Carbazole based compound；Two polystyrene-based (dimerized
Styryl) compound；BAlq；10- hydroxy benzo quinoline metal compound；BenzoAzoles, benzothiazole and benzimidazole system
Close object；Poly- (to phenylene vinylidene) (PPV) is macromolecule；Loop coil (spiro) compound；Polyfluorene, rubrene etc., but not
It is only limitted to this.
Above-mentioned luminescent layer may include material of main part and dopant material.Material of main part has aromatic fused ring derivative or contains
Heterocyclic compound etc..Specifically, having anthracene derivant, pyrene derivatives, naphthalene derivatives and five as aromatic fused ring derivative
Benzene derivative, phenanthrene compound, fluoranthene compound etc. have carbazole derivates, dibenzofurans derivative as nitrogen-containing heterocgcies
Object, ladder type furan compoundPyrimidine derivatives etc., but not limited to this.
As dopant material, have aromatic amine derivative, styrylamine compounds, boron complexes, fluoranthene compound,
Metal complex etc..Specifically, being the aromatic series with substituted or unsubstituted arylamino as aromatic amine derivative
Fused-ring derivatives, have pyrene with arylamino, anthracene,Two indeno pyrenes (Periflanthene) etc., as styryl amine
Compound is to replace to have the compound of at least one aryl vinyl on substituted or unsubstituted arylamine, by selected from aryl,
Substituent group more than one or two of silicyl, alkyl, naphthenic base and arylamino is substituted or unsubstituted.It is specific and
Speech, has styryl amine, styryl diamines, styryl triamine, styryl tetramine etc., but not limited to this.In addition,
As metal complex, there are complex of iridium, platinum complex etc., but not limited to this.
Above-mentioned electron transfer layer is from electron injecting layer reception electronics and by the layer of electron-transport to luminescent layer, as electronics
Transport materials are can to inject well electronics from cathode and transfer them to the substance of luminescent layer, the big object of electron mobility
Matter is suitable.As concrete example, there is the Al complex of 8-hydroxyquinoline, comprising Alq3Complex, organic free radical chemical combination
Object, flavonol-metal complex etc., it is not limited to this.Electron transfer layer can as used in the prior art that
Sample and the cathode substance of any desired are used together.In particular, the example of suitable cathode substance is with low work function and companion
There is the common substance of aluminium layer or silver layer.Specially caesium, barium, calcium, ytterbium and samarium, in every case with aluminium layer or silver layer.
Above-mentioned electron injecting layer is the layer for the electronics that injection carrys out self-electrode, preferably following compound: has transmission electronics
Ability, there is electron injection effect from cathode, for the excellent electron injection effect of luminescent layer or luminescent material, prevent
Only generated exciton is migrated to hole injection layer in luminescent layer, and film Forming ability is excellent.Specifically, have Fluorenone,
Anthraquinone bismethane (Anthraquinodimethane), diphenoquinone, thiopyrandioxide,Azoles,Diazole, triazole, imidazoles,
Tetrabasic carboxylic acid, fluorenylidene-methane, anthrone etc. and their derivative, metal complex and nitrogenous five-membered ring derivative
Deng but not limited to this.
As above-mentioned metal complex, there are 8-hydroxyquinoline lithium, bis- (8-hydroxyquinoline) zinc, bis- (8-hydroxyquinolines)
Copper, bis- (8-hydroxyquinoline) manganese, three (8-hydroxyquinoline) aluminium, three (2- methyl -8-hydroxyquinoline) aluminium, three (8-hydroxyquinolines)
Gallium, bis- (10- hydroxy benzo [h] quinoline) berylliums, bis- (10- hydroxy benzo [h] quinoline) zinc, bis- (2- methyl -8- quinoline) gallium chlorides,
Bis- (2- methyl -8- quinoline) (o-cresol) galliums, bis- (2- methyl -8- quinoline) (1- naphthols) aluminium, bis- (2- methyl -8- quinoline) (2-
Naphthols) gallium etc., but not limited to this.
According to used material, organic illuminating element according to the present invention can be top emission type, bottom emission type
Or bidirectional luminescence type.
In addition, the compound indicated by above-mentioned chemical formula 1 other than organic illuminating element, be further included in it is organic too
In positive energy battery or organic transistor.
Manufacture to the compound and the organic illuminating element comprising it that are indicated by above-mentioned chemical formula 1 in the examples below
It is concretely demonstrated.But following embodiments are for illustrating the present invention, it's not limited to that for the scope of the present invention.
[Production Example]
Production Example 1: the manufacture of compound A-1-1 to A-1-3
The manufacture of step 1) compound A-1-1
[the fluorenes] -2- of 9,9'- spiral shell two alcohol (150g, 465mmol) is added in DMF (400ml) after dissolution, is delayed at 0 DEG C
It is slow that NBS (83.5g, 469mmol) is added dropwise, it is stirred at room temperature 3 hours.After being extracted at normal temperature with water and chloroform, by white
Solid hexane recrystallizes and has manufactured above compound A-1-1 (162g, yield 85%).
MS[M+H]+=412.30
The manufacture of step 2) compound A-1-2
Under nitrogen atmosphere by above compound A-1-1 (30g, 72.9mmol), bis- (pinacol combined) two boron (22.23g,
It 87.5mmol) is mixed with potassium acetate (25.06g, 255.2mmol), addition twoAlkane (300ml) heats while stirring.It is flowing back
Under state, bis- (dibenzalacetone) palladiums (840mg, 0.02mol%) are added and tricyclohexyl phosphine (820mg, 0.04mol%) adds
Heat simultaneously stirs 3 hours.After reaction, it is filtered after cooling the temperature to room temperature.Water is poured into filtered fluid, is extracted with chloroform, is had
Machine layer is dry with anhydrous magnesium sulfate.It is recrystallized after vacuum distillation with ethyl acetate and hexane and has manufactured above compound A-1-2
(28.4g, 85%).
MS[M+H]+=459.36
The manufacture of step 3) compound A-1-3
Above compound A-1-2 (30g, 65.5mmol) is put into 2M sodium hydroxide solution, in 0 DEG C of stabilization processes
Afterwards, hydrogen peroxide (25ml, 131.18mmol) is added while stirring and completes to react.After reaction, investment water stirring 30
Room temperature is cooled the temperature to after minute, to manufacture above compound A-1-3 (18.28g, yield 80%).
MS[M+H]+=349.30
Production Example 2: the manufacture of compound B-1-1 to B-1-6
Production Example 2-1: the manufacture of compound B-1-1
3,4- dihydroxy -9H- fluorenes -9- ketone (30g, 141.3mmol), bromo- 1, the 2- difluoro of 4- are added in DMF (300ml)
Benzene (40.93g, 212.06mmol) and potassium carbonate (82.06g, 593.7mmol) flow back and stir.Temperature is dropped after reaction
To room temperature and filter.At normal temperature with after water and chloroform extraction, white solid ethyl acetate and hexane have been subjected to column chromatography,
To manufacture above compound B-1-1 (18.06g, yield 35%).
MS[M+H]+=366.18
Production Example 2-2: the manufacture of compound B-1-2
In the manufacture of above-mentioned B-1-1, compound B-1-2 has been manufactured by column chromatography for separation.
MS[M+H]+=366.18
Production Example 2-3: the manufacture of compound B-1-3
Bromo- 1, the 2- difluorobenzene of 4- is replaced to pass through the system with compound B-1-1 in addition to this using bromo- 2, the 3- difluorobenzene of 1-
It makes the identical method of method to be manufactured, to manufacture B-1-3.
MS[M+H]+=366.18
Production Example 2-4: the manufacture of compound B-1-4
In above-mentioned B-1-3 manufacture, compound B-1-4 has been manufactured by column chromatography for separation.
MS[M+H]+=366.18
Production Example 2-5: the manufacture of compound B-1-5
Using chloro- 4, the 5- difluorobenzene of 1,2- bis- replace bromo- 1, the 2- difluorobenzene of 4-, in addition to this, by with compound B-1-1
The identical method of manufacturing method manufactured, to manufacture B-1-5.
MS[M+H]+=356.17
Production Example 2-6: the manufacture of compound B-1-6
Using chloro- 2, the 3- difluorobenzene of Isosorbide-5-Nitrae-two replace bromo- 1, the 2- difluorobenzene of 4-, in addition to this, by with compound B-1-1
The identical method of manufacturing method manufactured, to manufacture B-1-6.
MS[M+H]+=356.17
Production Example 3: the manufacture of compound A1 to A6
Production Example 3-1: the manufacture of compound A1
3,4- dihydroxy -9H- fluorenes -9- ketone is replaced using compound A-1-3, in addition to this, by with compound B-1-1's
The identical method of manufacturing method is manufactured, to manufacture compound A1.
MS[M+H]+=502.38
Production Example 3-2: the manufacture of compound A2
3,4- dihydroxy -9H- fluorenes -9- ketone is replaced using compound A-1-3, in addition to this, by with compound B-1-2's
The identical method of manufacturing method is manufactured, to manufacture compound A1.
MS[M+H]+=502.38
Production Example 3-3: the manufacture of compound A-13
3,4- dihydroxy -9H- fluorenes -9- ketone is replaced using compound A-1-3, in addition to this, by with compound B-1-3's
The identical method of manufacturing method is manufactured, to manufacture compound A1.
MS[M+H]+=502.38
Production Example 3-4: the manufacture of compound A4
3,4- dihydroxy -9H- fluorenes -9- ketone is replaced using compound A-1-3, in addition to this, by with compound B-1-4's
The identical method of manufacturing method is manufactured, to manufacture compound A4.
MS[M+H]+=502.38
Production Example 3-5: the manufacture of compound A-45
3,4- dihydroxy -9H- fluorenes -9- ketone is replaced using compound A-1-3, in addition to this, by with compound B-1-5's
The identical method of manufacturing method is manufactured, to manufacture compound A-45.
MS[M+H]+=492.37
Production Example 3-6: the manufacture of compound A6
3,4- dihydroxy -9H- fluorenes -9- ketone is replaced using compound A-1-3, in addition to this, by with compound B-1-6's
The identical method of manufacturing method is manufactured, to manufacture compound A6.
MS[M+H]+=492.37
Production Example 4: the manufacture of compound B-11 to B6
Production Example 4-1: the manufacture of compound B-11
After 2- aminobphenyl (80.2mmol) is dissolved in THF (250ml), -78 DEG C are cooled the temperature to, 2.5M is then added dropwise
N-BuLi (n-BuLi) (9ml) is added compound B-1-1 (80.2mmol) after stirring 30 minutes, improves to room temperature, stirs
It mixes 1 hour.The HCl (100ml) of 1N is added, after stirring 30 minutes, carry out layer separation and after removing solvent, with ethyl acetate and oneself
Alkane carries out column chromatography, with re-crystallizing in ethyl acetate, filters and dry.Then dry solid is added in acetic acid (300ml)
Afterwards, it heats and stirs, after sulfuric acid (1ml) is added dropwise, flow back 3 hours.It filters, recrystallize after reaction, to manufacture chemical combination
Object B1.
MS[M+H]+=502.38
Production Example 4-2: the manufacture of compound B2
Compound B-1-1 is replaced to pass through method identical with the manufacturing method of compound B-11 in addition to this using B-1-2
Compound B2 is manufactured.
MS[M+H]+=502.38
Production Example 4-3: the manufacture of compound B3
Compound B-1-1 is replaced to pass through method identical with the manufacturing method of compound B-11 in addition to this using B-1-3
Compound B3 is manufactured.
MS[M+H]+=502.38
Production Example 4-4: the manufacture of compound B4
Compound B-1-1 is replaced to pass through method identical with the manufacturing method of compound B-11 in addition to this using B-1-4
Compound B4 is manufactured.
MS[M+H]+=502.38
Production Example 4-5: the manufacture of compound B5
Compound B-1-1 is replaced to pass through method identical with the manufacturing method of compound B-11 in addition to this using B-1-5
Compound B5 is manufactured.
MS[M+H]+=492.37
Production Example 4-6: the manufacture of compound B-26
Compound B-1-1 is replaced to pass through method identical with the manufacturing method of compound B-11 in addition to this using B-1-6
Compound B-26 is manufactured.
MS[M+H]+=492.37
[embodiment]
Embodiment 1: the manufacture of compound 1
In dimethylbenzene be added compound A1 (15g, 29.9mmol), two ([1,1'- biphenyl] -4- base) amine (9.81g,
It 30.5mmol) with sodium tert-butoxide (4.03g, 41.8mol), heats and flows back after stirring, [bis- (tri-tert-butylphosphines)] palladium is added
(170mg, 1mol%).Room temperature is cooled the temperature to, after reaction was completed, using tetrahydrofuran and re-crystallizing in ethyl acetate, to make
Compound 1 (16.4g, yield 74%) is made.
MS[M+H]+=742.89
Embodiment 2: the manufacture of compound 2
Using compound A2 replace compound A1, using 9,9- dimethyl-N-phenyl -9H- fluorenes -2- amine replace two ([1,
1'- biphenyl] -4- base) amine manufactured, to manufacture in addition to this by method identical with the manufacturing method of compound 1
Compound 2.
MS[M+H]+=706.86
Embodiment 3: the manufacture of compound 3
Compound A1 is replaced using compound A-13, uses N- ([1,1'- diphenyl] -2- base) -9,9- dimethyl -9H- fluorenes -
2- amine replaces two ([1,1'- biphenyl] -4- base) amine, in addition to this, is carried out by method identical with the manufacturing method of compound 1
Manufacture, to manufacture compound 3.
MS[M+H]+=782.96
Embodiment 4: the manufacture of compound 4
Compound A1 is replaced using compound A4, uses N- ([1,1'- biphenyl] -4- base)-(1,1'；4', 1'- terphenyl
Base) -4- amine replace two ([1,1'- biphenyl] -4- base) amine pass through method identical with the manufacturing method of compound 1 in addition to this
It is manufactured, to manufacture compound 4.
MS[M+H]+=818.99
Embodiment 5: the manufacture of compound 5
The manufacture of step 1) compound int.1
Using compound A2 replace compound A-2-1, using 3- chlorophenylboronic acid replace the chloro- 1- iodobenzene of the bromo- 4- of 2-, except this with
Outside, it is manufactured by method identical with the manufacturing method of compound A-3-1, to manufacture compound int.1.
MS[M+H]+=534.02
The manufacture of step 2) compound 5
In the manufacture of above compound 1, compound A1 is replaced using compound int.1, uses N- phenyl-[1,1'- connection
Benzene] -2- amine replace two ([1,1'- biphenyl] -4- base) amine pass through method identical with the manufacturing method of compound 1 in addition to this
It is manufactured, to manufacture compound 5.
MS[M+H]+=756.87
Embodiment 6: the manufacture of compound 6
The manufacture of step 1) compound int.4
In the manufacture of above compound int.1, compound A2 is replaced using compound A-13, uses (4'- chloro- [1,1'-
Biphenyl] -3- base) boric acid replace 3- chlorophenylboronic acid pass through method identical with the manufacturing method of compound int.1 in addition to this
It is manufactured, to manufacture compound int.4.
MS[M+H]+=610.12
The manufacture of step 2) compound 6
In the manufacture of above compound 1, compound A1 is replaced using compound int.4, replaces two using diphenylamines
([1,1'- biphenyl] -4- base) amine is manufactured by method identical with the manufacturing method of compound 1 in addition to this, thus
Compound 6 is manufactured.
MS[M+H]+=742.89
Embodiment 7: the manufacture of compound 7
In the manufacture of above compound 1, using compound A-45 replace compound A1, using diphenylamines replace two ([1,
1'- biphenyl] -4- base) amine manufactured, to manufacture in addition to this by method identical with the manufacturing method of compound 1
Compound 7.
MS[M+H]+=757.91
Embodiment 8: the manufacture of compound 8
In the manufacture of above compound 1, using compound A6 replace compound A1, using diphenylamines replace two ([1,
1'- biphenyl] -4- base) amine manufactured, to manufacture in addition to this by method identical with the manufacturing method of compound 1
Compound 8.
MS[M+H]+=757.91
Embodiment 9: the manufacture of compound 9
Using compound B-11 replace compound A1, in addition to this, by method identical with the manufacturing method of compound 1 into
Row manufacture, to manufacture compound 9.
MS[M+H]+=742.89
Embodiment 10: the manufacture of compound 10
In the manufacture of above compound 1, compound A1 is replaced using compound B2, uses N, 9,9- triphenyl -9H-
Fluorenes -4- amine replaces two ([1,1'- biphenyl] -4- base) amine to pass through method identical with the manufacturing method of compound 1 in addition to this
It is manufactured, to manufacture compound 10.
MS[M+H]+=831.00
Embodiment 11: the manufacture of compound 11
In the manufacture of above compound 1, compound A1 is replaced using compound B3, uses N- ([1,1'- biphenyl] -4-
Base)-(1,1'- biphenyl) -2- amine replace two ([1,1'- biphenyl] -4- base) amine pass through the manufacturer with compound 1 in addition to this
The identical method of method is manufactured, to manufacture compound 11.
MS[M+H]+=742.89
Embodiment 12: the manufacture of compound 12
In the manufacture of above compound 1, compound A1 is replaced using compound B4, uses N- phenyl-[1,1；4',1'-
Terphenyl] -4- amine is instead of two ([1,1'- biphenyl] -4- base) amine, in addition to this, by identical as the manufacturing method of compound 1
Method manufactured, to manufacture compound 12.
MS[M+H]+=742.89
Embodiment 13: the manufacture of compound 13
A-2-1 is replaced using compound B5, uses N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxa boron
Heterocycle pentane -2- base) aniline replace the chloro- 1- iodobenzene of the bromo- 4- of 2- pass through the manufacturer with above compound A-3-1 in addition to this
The identical method of method is manufactured, to manufacture compound 13.
MS[M+H]+=910.10
Embodiment 14: the manufacture of compound 14
In the manufacture of above compound 1, compound 1 is replaced using compound B-26, uses N- benzene-[1,1'- biphenyl] -2-
Amine replaces two ([1,1'- biphenyl] -4- base) amine to pass through method system identical with the manufacturing method of compound 1 in addition to this
It makes, to manufacture compound 14.
MS[M+H]+=910.10
Embodiment 15: the manufacture of compound 15
In the manufacture of above compound 1, compound A1 is replaced using compound C1, uses N- phenyl-[1,1'- connection
Benzene] -2- amine replace two ([1,1'- biphenyl] -4 bases) amine pass through method identical with the manufacturing method of compound 1 in addition to this
It is manufactured, to manufacture compound 15.
MS[M+H]+=666.79
Experimental example 1-1
It will be withThickness thin film be coated with the glass substrate (healthy and free from worry 7059 glass) of ITO (tin indium oxide) and be put into
In distilled water dissolved with dispersing agent, washed using ultrasonic wave.Detergent is made using Fei Xier company (Fischer Co.)
Product, distilled water have used the steaming of filter (Filter) filtering for utilizing Millipore Corp. (Millipore Co.) to manufacture twice
Distilled water.After ITO is washed 30 minutes, it is repeated twice with distilled water and carries out 10 minutes ultrasonic washings.In distillation water washing knot
Shu Hou carries out ultrasonic washing and drying with the solvent sequence of isopropanol, acetone, methanol.
On the ito transparent electrode prepared in this way, by following HAT compounds withThickness carry out thermal vacuum vapor deposition
And form hole injection layer.Chemical combination of the vacuum evaporation as the above-mentioned manufacture of the substance of transporting holes on above-mentioned hole injection layer
Object 1Afterwards, then on above-mentioned hole transmission layer withThe following HT2 compounds of film thickness vacuum evaporation and shape
At hole regulating course.On above-mentioned hole regulating course by following H1 compounds (main body) and following D1 compounds (dopant) with
The weight ratio of 25:1 carries out vacuum evaporation and is formedThe luminescent layer of thickness.Then, by following E1 compounds
It is deposited with the ratio of LiQ using 1:1 and successively carries out thermal vacuum vapor deposition as electron injection and transport layer.It is passed in above-mentioned electronics
On defeated layer successively by lithium fluoride (LiF) withThickness, by aluminium withThickness is deposited and forms cathode, thus
Organic illuminating element is manufactured.
In above process, the evaporation rate of organic matter maintainsLithium fluoride maintainsVapor deposition speed
Degree, aluminium maintainEvaporation rate, vapor deposition when, vacuum degree maintain 1 × 10-7~5 × 10-8Support.
Experimental example 1-2 to 1-15
It is manufactured by method identical with above-mentioned experimental example 1-1, is replaced using the compound by being recorded in following table 1
Compound 1 has manufactured organic illuminating element by identical method in addition to this.
Comparative experiments example 1-1 to 1-6
It is manufactured by method identical with above-mentioned experimental example 1-1, uses the compound replacementization recorded in following table 1
It closes object 1 and organic illuminating element has been manufactured by identical method in addition to this.In following table 1, HT1, HT3, HT4 are respectively such as
Shown in lower.
Comparative experiments example 1-4
It is manufactured by method identical with above-mentioned experimental example 1-1, as hole transmission layer, uses following HT3 chemical combination
Object replaces compound 1, as hole regulating course, compound HT2 is replaced using following HT5 compounds, in addition to this, by identical
Method manufactured organic illuminating element.
Comparative experiments example 1-5 and 1-6
It is manufactured by method identical with above-mentioned experimental example 1-1, is replaced using the compound by being recorded in following table 1
Compound 1 has manufactured organic illuminating element by identical method in addition to this.In following table 1, HT7 and HT8 are respectively such as
Shown in lower.
Electric current applied to the organic illuminating element that manufactures in above-mentioned experimental example and comparative experiments example, measurement driving voltage and
Efficiency the results are shown in following table 1.At this moment, brightness is reduced to 95% institute when the service life is defined as original intensity being set as 100%
The time needed.
[table 1]
Experimental example 2-1
It will be withThickness thin film be coated with the glass substrate (healthy and free from worry 7059 glass) of ITO (tin indium oxide) and be put into
In distilled water dissolved with dispersing agent, washed using ultrasonic wave.Detergent is made using Fei Xier company (Fischer Co.)
Product, distilled water have used the steaming of filter (Filter) filtering for utilizing Millipore Corp. (Millipore Co.) to manufacture twice
Distilled water.After ITO is washed 30 minutes, it is repeated twice with distilled water and carries out 10 minutes ultrasonic washings.In distillation water washing knot
Shu Hou carries out ultrasonic washing and drying with the solvent sequence of isopropanol, acetone, methanol.
On the ito transparent electrode prepared in this way, by following HAT compounds withThickness carry out thermal vacuum vapor deposition
And form hole injection layer.Following HT1 compounds of the vacuum evaporation as the substance of transporting holes on above-mentioned hole injection layerAfterwards, then on above-mentioned hole transmission layer withThe above-mentioned manufacture of film thickness vacuum evaporation compound 1 and shape
At hole regulating course.On above-mentioned hole regulating course by following H1 compounds (main body) and following D1 compounds (dopant) with
The weight ratio of 25:1 carries out vacuum evaporation and is formedThe luminescent layer of thickness.Then, by following E1 compounds
Thermal vacuum vapor deposition is successively carried out as electron injection and transport layer.On above-mentioned electron transfer layer successively by lithium fluoride (LiF) withThickness, by aluminium withThickness be deposited and form cathode, to manufacture organic illuminating element.
In above process, the evaporation rate of organic matter maintainsLithium fluoride maintainsVapor deposition speed
Degree, aluminium maintainEvaporation rate, vapor deposition when, vacuum degree maintain 1 × 10-7To 5 × 10-8Support.
Experimental example 2-2 to 2-17
It is manufactured by method identical with above-mentioned experimental example 2-1, uses the compound replacementization recorded in following table 2
It closes object 1 and organic illuminating element has been manufactured by identical method in addition to this.
Comparative experiments example 2-1 to 2-6
It is manufactured by method identical with above-mentioned experimental example 2-1, respectively using the compound generation recorded in following table 2
For compound HT1 and compound 1, in addition to this, organic illuminating element is manufactured by identical method.In following table 2, HT3,
HT4, HT5, HT6 difference are as follows.
Electric current applied to the organic illuminating element that manufactures in above-mentioned experimental example and comparative experiments example, measurement driving voltage and
Efficiency the results are shown in following table 2.At this moment, brightness is reduced to 95% institute when the service life is defined as original intensity being set as 100%
The time needed.
[table 2]
The compound derivatives of chemical formula according to the present invention are using organic illuminating element as the organic electronic element of representative
In can play the role of hole transport and hole and adjust, element according to the present invention is in terms of efficiency, driving voltage, stability
Show excellent characteristic.
[symbol description]
1: substrate 2: anode
3: luminescent layer 4: cathode
5: hole injection layer 6: hole transmission layer
7: luminescent layer 8: electron transfer layer.
Claims (8)
1. a kind of compound indicated by following chemical formula 1:
Compound 1
In the chemical formula 1,
X1To X4In, X1And X2、X2And X3Or X3And X4It being connect respectively with the * of following chemical formula 2, remaining is hydrogen,
Chemical formula 2
A, the integer that c, d and e are 0 to 3,
The integer that b is 0 to 2,
X is 1 or 2,
R1To R5It is each independently hydrogen, deuterium, halogen group, cyano, substituted or unsubstituted C1-60It is alkyl, substituted or unsubstituted
C1-60Alkoxy, substituted or unsubstituted C1-60Alkylthio, substituted or unsubstituted C3-60It is naphthenic base, substituted or unsubstituted
C6-60Aryl or three (C1-60Alkyl) silicyl,
R is to be indicated each independently by following chemical formula 3,
Chemical formula 3
In the chemical formula 3,
L1、L2And L3It is each independently singly-bound；Substituted or unsubstituted C6-60Arlydene；Or it is substituted or unsubstituted comprising selecting
From in N, O and S any one or more person heteroatomic C2-60Inferior heteroaryl,
Ar1And Ar2It is each independently substituted or unsubstituted C6-60Aryl；Or it is substituted or unsubstituted comprising selected from N, O and
In S any one or more person heteroatomic C2-60Heteroaryl.
2. compound according to claim 1, wherein the chemical formula 1 is indicated by following chemical formula 1-1,1-2 or 1-3:
Chemical formula 1-1
Chemical formula 1-2
Chemical formula 1-3
3. compound according to claim 1, wherein a, b, c, d and e are 0.
4. compound according to claim 1, wherein L1For singly-bound, phenylene, biphenyl diyl, terphenyl diyl, tetrad
Benzene diyl, naphthalene-diyl, anthracene diyl, luxuriant and rich with fragrance diyl, triphenylene diyl, pyrene diyl, dimethyl fluorene diyl, aminomethyl phenyl fluorenes diyl, two
Phenyl fluorenes diyl, dibenzofurans diyl, dibenzothiophenes diyl, carbazole diyl or 9- phenyl -9H- carbazole diyl.
5. compound according to claim 1, wherein L2And L3It is each independently singly-bound, phenylene, biphenyl diyl, three
Biphenyl diyl, quaterphenyl diyl, naphthalene-diyl, anthracene diyl, luxuriant and rich with fragrance diyl, triphenylene diyl, pyrene diyl, dimethyl fluorene diyl, methyl
Phenyl fluorenes diyl, diphenylfluorene diyl, spiro fluorene diyl, dibenzofurans diyl, dibenzothiophenes diyl, carbazole diyl or 9-
Phenyl -9H- carbazole diyl.
6. compound according to claim 1, wherein Ar1And Ar2Be each independently phenyl, xenyl, terphenyl,
Tetrad phenyl, naphthalene, phenanthryl, dimethyl fluorenyl, dibenzo fluorenyl, Spirofluorene-based, dibenzofuran group, dibenzothiophene, click
Oxazolyl or 9- phenyl -9H- carbazyl.
7. compound according to claim 1, wherein the compound indicated by the chemical formula 1 is selected from following chemical combination
Any of object:
8. a kind of organic illuminating element comprising: first electrode, it is opposed with the first electrode and have second electrode,
And have one layer or more of organic matter layer between the first electrode and the second electrode, in the organic matter layer
One layer or more includes compound described in any one of claims 1 to 7.
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| KR1020180062161A KR102109789B1 (en) | 2017-10-19 | 2018-05-30 | Novel compound and organic light emitting device comprising the same |
| PCT/KR2018/006423 WO2019078443A1 (en) | 2017-10-19 | 2018-06-05 | Novel compound and organic light emitting device using same |
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| CN111303113A (en) * | 2019-12-19 | 2020-06-19 | 陕西莱特光电材料股份有限公司 | Organic compound, electronic device, and electronic apparatus |
| CN112010866A (en) * | 2020-09-07 | 2020-12-01 | 京东方科技集团股份有限公司 | Dioxin compound and preparation method and application thereof |
| WO2021120838A1 (en) * | 2019-12-19 | 2021-06-24 | 陕西莱特光电材料股份有限公司 | Organic compound, electronic device, and electronic apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016131521A1 (en) * | 2015-02-16 | 2016-08-25 | Merck Patent Gmbh | Spirobifluorene derivative-based materials for electronic devices |
| WO2017111544A1 (en) * | 2015-12-24 | 2017-06-29 | 주식회사 두산 | Organic compound and organic electroluminescent device comprising same |
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| KR20140015226A (en) * | 2013-12-19 | 2014-02-06 | 주식회사 엘지화학 | New compounds and organic electronic device using the same |
| KR101614599B1 (en) * | 2014-04-09 | 2016-04-21 | 주식회사 두산 | Organic compound and organic electroluminescent device comprising the same |
| KR101863942B1 (en) * | 2015-08-28 | 2018-07-06 | 삼성디스플레이 주식회사 | Condensed-cyclic compound and organic light emitting device comprising the same |
-
2018
- 2018-06-05 CN CN201880018312.1A patent/CN110494430B/en active Active
- 2018-06-05 WO PCT/KR2018/006423 patent/WO2019078443A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016131521A1 (en) * | 2015-02-16 | 2016-08-25 | Merck Patent Gmbh | Spirobifluorene derivative-based materials for electronic devices |
| WO2017111544A1 (en) * | 2015-12-24 | 2017-06-29 | 주식회사 두산 | Organic compound and organic electroluminescent device comprising same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303113A (en) * | 2019-12-19 | 2020-06-19 | 陕西莱特光电材料股份有限公司 | Organic compound, electronic device, and electronic apparatus |
| WO2021120838A1 (en) * | 2019-12-19 | 2021-06-24 | 陕西莱特光电材料股份有限公司 | Organic compound, electronic device, and electronic apparatus |
| US11605784B2 (en) | 2019-12-19 | 2023-03-14 | Shaanxi Lighte Optoelectronics Material Co., Ltd. | Organic compound, electronic element, and electronic device |
| CN112010866A (en) * | 2020-09-07 | 2020-12-01 | 京东方科技集团股份有限公司 | Dioxin compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019078443A1 (en) | 2019-04-25 |
| CN110494430B (en) | 2022-05-27 |
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