New compound and organic luminescent device comprising it
阅读说明：本技术 新型化合物及包含其的有机发光器件 (New compound and organic luminescent device comprising it ) 是由 姜敏英 文程昱 朴胎润 李征夏 郑珉祐 赵圣美 蔡美荣 于 2018-07-04 设计创作，主要内容包括：本发明提供新型化合物及利用其的有机发光元件。(The present invention provides new compound and the organic illuminating element using it.)
1. a kind of compound indicated by following chemical formula 1 or 2:
Chemical formula 1
Chemical formula 2
In the chemical formula 1 and 2,
X is O or S,
L1And L2It is each independently singly-bound；Substituted or unsubstituted C6-60Arlydene；Or substituted or unsubstituted include 1 or more the heteroatomic C in O, N, Si and S2-60Inferior heteroaryl,
Ar is substituted or unsubstituted C6-60Aryl；Or substituted or unsubstituted includes 1 to 3 miscellaneous in N, O and S The C of atom2-60Heteroaryl,
R1To R5It is each independently hydrogen；Deuterium；Halogen；Cyano；Nitro；Amino；Substituted or unsubstituted C1-60Alkyl；Replace or Unsubstituted C1-60Halogenated alkyl；Substituted or unsubstituted C1-60Alkoxy；Substituted or unsubstituted C1-60Halogenated alkoxy；It takes Generation or unsubstituted C3-60Naphthenic base；Substituted or unsubstituted C2-60Alkenyl；Substituted or unsubstituted C6-60Aryl；Replace or not Substituted C6-60Aryloxy group；Or substituted or unsubstituted includes 1 or more the heteroatomic C in N, O and S2-60Heteroaryl Base,
A1 to a5 is each independently 0 to 2 integer.
2. compound according to claim 1, wherein L1And L2It is each independently singly-bound or phenylene.
3. compound according to claim 1, wherein Ar is selected from any of following radicals:
In the group,
Y is O, S or CZ4Z5,
Z1To Z5It is each independently hydrogen, deuterium, halogen, cyano, nitro, amino, C1-20Alkyl, C1-20Halogenated alkyl, C6-20Aryl, Heteroatomic C comprising 1 or more O or S2-20Heteroaryl,
N1 to n3 is each independently 0 to 3 integer.
4. compound according to claim 3, wherein Ar is selected from any of following radicals:
5. compound according to claim 1, wherein R1To R5For hydrogen, deuterium, halogen, cyano, C1-10Alkyl or C6-20 Aryl.
6. compound according to claim 1, wherein the compound is by following chemical formula 1-1 to 1-4 and 2-1 to 2-4 In one expression:
The chemical formula 1-1 to 1-4 and 2-1 into 2-4,
Explanation about X and Ar is identical as the definition in claim 1.
7. compound according to claim 1, wherein the compound is selected from any of following compounds:
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.
Technical field
With the mutual reference of related application
This application claims South Korea patent application the 10-2017-0088464th priority based on July 12nd, 2017, Full content as part of this specification disclosed in document comprising the South Korea patent application.
The present invention relates to new 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 layer comprising anode and cathode and between anode and cathode Structure.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 difference Substance constitute multilayered structure formed, for example, can by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, The formation such as electron injecting layer.For the structure of such organic electroluminescent device, 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.
Summary of the invention
Project to be solved
The present invention relates to new compound and include its organic illuminating element.
The solution of project
The present invention provides the compound indicated by following chemical formula 1 or 2:
[chemical formula 1]
[chemical formula 2]
In the chemical formula 1 and 2,
X is O or S,
L1And L2It is each independently singly-bound；Substituted or unsubstituted C6-60Arlydene；Or substituted or unsubstituted include 1 or more the heteroatomic C in O, N, Si and S2-60Inferior heteroaryl,
Ar is substituted or unsubstituted C6-60Aryl；Or substituted or unsubstituted includes 1 to 3 in N, O and S Heteroatomic C2-60Heteroaryl,
R1To R5It is each independently hydrogen；Deuterium；Halogen；Cyano；Nitro；Amino；Substituted or unsubstituted C1-60Alkyl；It takes Generation or unsubstituted C1-60Halogenated alkyl；Substituted or unsubstituted C1-60Alkoxy；Substituted or unsubstituted C1-60Halogenated alkoxy； Substituted or unsubstituted C3-60Naphthenic base；Substituted or unsubstituted C2-60Alkenyl；Substituted or unsubstituted C6-60Aryl；Replace or not Substituted C6-60Aryloxy group；Or substituted or unsubstituted includes 1 or more the heteroatomic C in N, O and S2-60Heteroaryl,
A1 to a5 is each independently 0 to 2 integer.
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 or 2 in above-mentioned organic matter layer.
Invention effect
It may be used as the material of the organic matter layer of organic illuminating element, In by the compound that above-mentioned chemical formula 1 or 2 indicates It can be realized the raising of efficiency, the raising of lower driving voltage and/or life characteristic in organic illuminating element.
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 is illustrated by substrate 1, anode 2, hole injection layer 5, hole transmission layer 6, luminescent layer 7,8 and of electron transfer layer The example for the organic illuminating element that cathode 4 is constituted.
Specific embodiment
In the following, being illustrated in more details to help to understand the present invention.
In this specification,Refer to that the key connecting with other substituent groups, singly-bound refer to by L1And L2On the part of expression not The case where there are other atoms.
In this specification, " substituted or unsubstituted " this term refers to by selected from deuterium；Halogen group；Cyano；Itrile group；Nitre Base；Hydroxyl；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)；Silicyl；Boryl；Alkyl；Ring Alkyl；Alkenyl；Aryl；Aralkyl；Arylalkenyl；Alkylaryl；Alkyl amine group；Aralkyl amido；Heteroaryl amido；Arylamine Base；Aryl phosphino-；Or comprising 1 or more the substituent group substitution in 1 or more in N, O and S atom heterocycle or not Replace, or the substituent group being formed by connecting by 2 or more substituent groups in foregoing illustrative substituent group is substituted or unsubstituted.Example Such as, " substituent group that 2 or more substituent groups are formed by connecting " can be xenyl.That is, xenyl can be aryl, it can also be by It is construed to 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 concrete example, there are vinyl, 1- third Alkenyl, 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 It's not limited to that.
In this specification, naphthenic base is not particularly limited, preferably carbon atom number be 3 to 60 naphthenic base.Implement according to one Mode, the carbon atom number of above-mentioned naphthenic base are 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 fluorenyl In substituted situation, Ke Yiwei Deng but not limited to this.
In this specification, heteroaryl is comprising 1 or more in O, N, Si and S as heteroatomic heteroaryl, carbon atom Number is not particularly limited, but preferably carbon atom number is 2 to 60.As the example of heteroaryl, have thienyl, furyl, pyrrole radicals, Imidazole radicals, thiazolyl,Oxazolyl,Di azoly, triazolyl, pyridyl group, bipyridyl, pyrimidine radicals, triazine radical, triazolyl, Acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, phthalazinyl, Pyridopyrimidine base, pyrido-pyrazine Base, pyrazine and pyrazinyl, isoquinolyl, indyl, carbazyl, benzoOxazolyl, benzimidazolyl, benzothiazolyl, benzo It is carbazyl, benzothienyl, dibenzothiophene, benzofuranyl, phenanthroline (phenanthroline), thiazolyl, different Oxazolyl,Di azoly, thiadiazolyl group, benzothiazolyl, 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 heteroaryl.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 heteroaryl 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 heteroaryl.
On the other hand, the present invention provides the compound indicated by above-mentioned chemical formula 1 or 2.
In above-mentioned chemical formula 1 and 2, L1And L2Singly-bound, substituted or unsubstituted phenylene, substitution can be each independently or do not taken The biphenylene in generation, substituted or unsubstituted naphthylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted anthrylene, substitution or Unsubstituted Asia fluoranthene base, substituted or unsubstituted sub- triphenylene, substituted or unsubstituted sub- pyrenyl, substituted or unsubstituted sub- click Oxazolyl, substituted or unsubstituted fluorenylidene or substituted or unsubstituted Asia are Spirofluorene-based
For example, L1And L2Singly-bound or phenylene can be each independently.
In addition, Ar can be substituted or unsubstituted C6-20Aryl or it is substituted or unsubstituted include 1 to 3 O or The heteroatomic C of S2-20Heteroaryl.
For example, Ar can be each independently selected from any of following radicals:
In above-mentioned group,
Y is O, S or CZ4Z5,
Z1To Z5It is each independently hydrogen, deuterium, halogen, cyano, nitro, amino, C1-20Alkyl, C1-20Halogenated alkyl, C6-20 Aryl, the heteroatomic C comprising 1 or more O or S2-20Heteroaryl,
N1 to n3 is each independently 0 to 3 integer.
At this moment, Z1To Z3It is each independently hydrogen, deuterium, phenyl or xenyl,
Z4And Z5Methyl or phenyl is each independently,
N1 to n3 is each independently 0,1 or 2.
Specifically, for example, Ar can be for selected from any of following radicals:
In addition, R1To R5Hydrogen, deuterium, halogen, cyano, C can be each independently1-10Alkyl or C6-20Aryl.
For example, R1To R5It can be each independently hydrogen, deuterium, halogen, cyano, methyl or phenyl, a1 to a5 can respectively solely It is on the spot 0 or 1.
Specifically, for example, R1To R5It can be hydrogen.
At this moment, a1 indicates R1Quantity, when a1 be 2 or more when, 2 or more R1It can be the same or different from each other.About a1 Explanation to a5 and n1 to n3 is referred to the structure of the above-mentioned explanation about a1 and above-mentioned chemical formula 1 or 2 to understand.
On the other hand, above compound can be indicated by following chemical formula 1-1 to 1-4 and 2-1 one into 2-4:
Above-mentioned chemical formula 1-1 to 1-4 and 2-1 into 2-4,
Explanation about X and Ar is identical as the definition in above-mentioned chemical formula 1 and 2.
For example, above compound can be for selected from any of following compounds:
The compound indicated by above-mentioned chemical formula 1 and 2 has the structure that amino is connected on No. 4 positions of fluorenes, thus Using the organic illuminating element of this compound and using the chemical combination with the structure for being connected with amino in the other positions of fluorenes The organic illuminating element of object is compared, and can have high efficiency, low driving voltage, high brightness and long-life etc..
It on the other hand, can be for example, by the manufacturer of following reaction equations 1 by the compound that above-mentioned chemical formula 1 or 2 indicates Method is manufactured.Above-mentioned manufacturing method can further embody in aftermentioned Production Example.
[reaction equation 1]
In above-mentioned reaction equation 1, L1、L2, Ar and X it is identical as above-mentioned definition.
Above-mentioned reaction, which may include, to be made by the above-mentioned chemical formula 1-a compound indicated and by above-mentioned chemical formula 1-b expression The step of compound reacts and manufactures the compound indicated by above-mentioned chemical formula 1.Above-mentioned reaction preferably exists as amine substitution reaction Implement in the case where having palladium catalyst and alkali, the reactive group (for example, X ' is halogen) for amine substitution reaction can be according to this Well known method changes in field.Above-mentioned manufacturing method can be more specific in aftermentioned Production Example.
The compound indicated by above-mentioned chemical formula 2 can refer to above-mentioned reaction equation 1 and the knot with the compound of desired manufacture Structure replaces initial substance suitably correspondingly to manufacture.
On the other hand, the present invention provides the organic illuminating element of the compound comprising being indicated by above-mentioned chemical formula 1 or 2.Make For an example, the present invention a kind of organic illuminating element is provided comprising, first electrode, it is opposed with above-mentioned first electrode and The second electrode that has and have one layer or more of organic matter layer between above-mentioned first electrode and above-mentioned second electrode, One layer or more the compound comprising being indicated by above-mentioned chemical formula 1 or 2 in above-mentioned organic matter 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 lesser amount of organic 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 other than luminescent layer also Comprising between above-mentioned first electrode and above-mentioned luminescent layer hole injection layer and hole transmission layer and above-mentioned luminescent layer with it is above-mentioned The structure of electron transfer layer and electron injecting layer as organic matter layer between second electrode.But the knot of organic illuminating element It's not limited to that for structure, may include less or more layer of organic layer.
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 Fig. 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 or 2 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, by the chemical combination of above-mentioned chemical formula 1 or 2 expression Object 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 Or 2 indicate compound other than, well known material and the method in the technical field of can use are manufactured.In addition, when above-mentioned In the case that organic illuminating element includes multiple organic matter layers, above-mentioned organic matter layer can be by identical substance or different substances It is formed.
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 is deposited on the organic matter layer later It can be used as the substance of 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, not only can use vacuum when manufacturing organic illuminating element by the compound that above-mentioned chemical formula 1 or 2 indicates Vapour deposition method can also form organic matter layer using solution coating method.Herein, so-called solution coating method refers to, spin-coating method, leaching Coating, 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)；ZnO:Al or SNO2: the metals such as Sb and oxide Combination；Poly- (3 methyl thiophene), poly- [3,4- (ethylidene -1,2- dioxy) thiophene] (PEDOT), polypyrrole and polyaniline etc. are led Electrical macromolecule etc., 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；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 It closes object: having the ability of transporting holes, there is 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 the mobility in hole is suitable.As concrete example, there are aryl amine system organic matter, electroconductive polymer, Yi Jitong When 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 can also spread out comprising aromatic fused ring Biology or nitrogen-containing heterocgcies etc..Specifically, having anthracene derivant, pyrene derivatives, naphthalene derivative as aromatic fused ring derivative Object, pentacene derivative, phenanthrene compound, fluoranthene compound etc. have carbazole derivates, dibenzo furan as nitrogen-containing heterocgcies It mutters derivative, 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 receive well electronics from cathode and transfer them to the substance of luminescent layer, and the mobility of electronics is big Substance is suitable.As concrete example, there is the Al complex of 8-hydroxyquinoline, comprising Alq3Complex, organic free radical Object, hydroxyl brass-metal complex etc. are closed, it is not limited to this.Electron transfer layer can be as used in the prior art It is used together like that with the cathode substance of any desired.In particular, the example of suitable cathode substance be with low work function and With the common substance with 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 or 2 has been further included in other than organic illuminating element In machine solar battery or organic transistor.
To the compound that is indicated by above-mentioned chemical formula 1 or 2 and include its organic illuminating element in the following embodiments Manufacture 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 intermediate A
The manufacture of step 1) compound A-1
By 2- bromophenyl Ethyl formate (15g, 65.5mmol) and 2- methoxyphenyl-boronic acid (10.5g, 68.8mmol) point It dissipates after tetrahydrofuran (200ml), adds the wet chemical (aq.K of 2M2CO3) (65ml, 130mmol), four (triphens are added Base phosphine) palladium [Pd (PPh3)4] after (760mg, 1mol%), return stirring 6 hours.Room temperature is cooled the temperature to, water layer is separated, will have Machine layer is further washed 1 time again with water, is carried out layer separation and is separated organic layer.Anhydrous slufuric acid is put into the organic layer of collection Magnesium is filtered after forming slurry, is concentrated under reduced pressure.Oily compound is passed through into silicagel column with the combination of hexane and ethyl acetate It is separated, to manufacture the solid compounds A-1 (13.6g, yield 81%) of white.
The manufacture of step 2) compound A-2
After compound A-1 (16g, 62mmol) is put into anhydrous tetrahydro furan (175mL) solution, ice bath is used (icebath) temperature for reducing above-mentioned solution, adds the methyl-magnesium-bromide tetrahydrofuran solution (190mL) of 1M, is stirred at room temperature 5 Hour.Water is added after reaction, is extracted with ethyl acetate, after organic layer is washed with water again, at anhydrous magnesium sulfate After managing and filtering, it is concentrated under reduced pressure.Obtained compound is divided with the combination of hexane and ethyl acetate by silicagel column From to manufacture target compound A-2 (13.0g, yield 86%).
The manufacture of step 3) compound A-3
After compound A-2 (15g, 62mmol) is put into the acetic acid of 150mL, the concentrated sulfuric acid of 3mL is put into, is heated to 60 DEG C and stir 3 hours.It is cooled to room temperature after reaction, the solid of precipitation is filtered.The solid of filtering is dissolved in second Acetoacetic ester is washed with saturated aqueous solution of sodium bicarbonate, and collected organic layer is dried with anhydrous magnesium sulfate, is depressurized after filtering dense Contracting.Ethyl alcohol and hexane are added in the compound of concentration and solid is precipitated, and are filtered after forming slurry, to manufacture target chemical combination Object A-3 (10.1g, yield 73%).
The manufacture of step 4) compound A-4
Compound A-3 (13.8g, 61.5mmol) is put into tetrahydrofuran (140mL), temperature is reduced to -70 DEG C, It is slowly added the lithium hexane solution (44mL) of 1.6M and stirs 1 hour.Triisopropyl borate ester is added dropwise in the mixture Temperature is warmed to room temperature and stirs 5 hours by (12.3,61.7mmol).The hydrochloric acid of 2M is added in obtained reaction solution, in room temperature Lower stirring 3 hours.Mixture is extracted with ethyl acetate, organic layer is washed with water 2 times, is done with anhydrous sodium sulfate It is dry, solvent is concentrated under reduced pressure.The compound hexane and ethyl alcohol of concentration are formed into slurry, after filtering product, manufacture Target compound A-4 (11.6g, yield 70%).
The manufacture of step 5) compound A-5
Tetrahydrofuran is dispersed by the fluoro- 3- iodobenzene (16.8g, 56mmol) of compound A-4 (15g, 56mmol) and the bromo- 2- of 1- After (150ml), the wet chemical (aq.K of 2M is added2CO3) (56ml, 112mmol), tetrakis triphenylphosphine palladium [Pd is added (PPh3)4] after (650mg, 1mol%), return stirring 6 hours.Room temperature is cooled the temperature to, water layer is separated, organic layer is used again Water further washs 1 time and separates organic layer.Anhydrous magnesium sulfate is put into the organic layer of collection after forming slurry, is carried out Filter is concentrated under reduced pressure.The compound ethyl acetate and ethyl alcohol recrystallization that will be obtained, to manufacture target compound A-5 (15.7g, yield 77%).
The manufacture of step 6) compound A-6
Compound A-5 (15g, 37.8mmol) is put into the dichloromethane solution of 150mL, the temperature of solution is cooling To -70 DEG C, the Boron tribromide dichloromethane solution 50mL of 1M is slowly added dropwise, after being warming up to room temperature, stirs 5 hours.Reaction terminates Afterwards, in the mixture plus water, it is extracted with methylene chloride, organic layer is washed with water.With the dry organic layer of anhydrous magnesium sulfate, mistake It filters and is concentrated under reduced pressure.The concentrate made with a small amount of ethyl acetate filters after forming slurry, to obtain target chemical combination Object A-6 (12g, yield 83%).
The manufacture of step 7) intermediate A
Compound A-6 (24g, 63mmol) is diluted in the n-methyl-2-pyrrolidone of 120mL, puts into carbonic acid Potassium (17.3g, 63mmol), is heated to 140 DEG C.After about 1 hour, reactant is cooled to room temperature, slowly puts into the water of 1.2L In.The solid of precipitation is filtered, after being dissolved in tetrahydrofuran, is handled with anhydrous magnesium sulfate, is concentrated under reduced pressure after filtering. It is filtered after making the compound formation slurry of concentration with a small amount of tetrahydrofuran and excessive hexane.In order to the compound that will filter into Row purifying, separated with hexane and ethyl acetate by silicagel column, thus manufactured intermediate A (14.7g, yield 65%, MS:[M+H]+=364).
Production Example 2: the manufacture of intermediate B
In the synthesis example of the compound A-5 of intermediate A Production Example, the bromo- 2- of 1- is replaced using the fluoro- 2- iodobenzene of the bromo- 3- of 1- Fluoro- 3- iodobenzene is tested, to manufacture intermediate B in addition to this by method identical with the synthesis example of intermediate A.
Production Example 3: the manufacture of intermediate C
The manufacture of step 1) compound C-1
Using the bromo- 5- chloro benzoic ether of compound 2- (methyl 2-bromo-5-chlorobenzoate) (25g, 100mmol) and dibenzo [b, d] furans -4- ylboronic acid (dibenzo [b, d] furan-4-ylboronic acid) (21.2g, 100mmol), by method identical with the Production Example of intermediate A -1 is tested manufactured compound C-1 (27g, 80%).
The manufacture of step 2) compound C-2
Using compound C-1 (25g, 74mmol), tested by method identical with the Production Example of compound A-2, To manufacture compound C-2 (18g, 72%).
The manufacture of step 3) intermediate C
Using compound C-2 (15g, 44.5mmol), carried out by method identical with the Production Example of compound A-3 real Test, thus manufactured intermediate C (10.4g, 73%, MS:[M+H]+=319).
Production Example 4
The manufacture of step 1) compound 1-1
Intermediate A (20g, 55mmol) and [1,1'- xenyl] -4- amine (9.8g, 58mmol) are put into the first of 200mL Benzene and dissolve, addition sodium tert-butoxide (10.5g, 110mmol) simultaneously heat.Bis- (tri-tert-butylphosphine) palladiums (0.3g, 1mol%) are put into, Return stirring 3 hours.Toluene is concentrated under reduced pressure after reaction, the mixture of concentration is dissolved in the chloroform of 300mL, is washed with water 2 times.Organic layer is separated, anhydrous magnesium sulfate is added, is filtered after stirring, is evaporated under reduced pressure filtrate.The compound of concentration is passed through into silica gel Column chromatography is purified, to manufacture compound 1-1 (18.1g, yield 73%).
The manufacture of step 2) compound 1-2
By the bromo- 9,9- dimethyl -9H- fluorenes (20g, 73.2mmol) of 4- and (4- chlorphenyl) boric acid (12.6g, 80.5mmol) After being scattered in tetrahydrofuran (200ml), the solution of potassium carbonate (aq.K of 2M is added2CO3) (73ml, 143mmol), four (triphens are added Base phosphine) palladium [Pd (PPh3)4] after (850mg, 1mol%), return stirring 6 hours.Room temperature is cooled the temperature to, water layer is separated, will have Machine layer further washs 1 time with water again and separates organic layer.Anhydrous magnesium sulfate is put into the organic layer of collection and forms slurry It after material, is filtered, is concentrated under reduced pressure.The compound ethyl alcohol recrystallization that will be obtained, to manufacture compound 1-2 (18.0g, 81%).
The manufacture of step 3) compound 1
Compound 1-1 (20g, 44mmol) and compound 1-2 (14.2g, 46.5mmol) are put into the dimethylbenzene of 200ml In, it makes it dissolve, adds sodium tert-butoxide (18.8g, 88.6mmol) and heat.Bis- (tri-tert-butylphosphine) palladiums of investment (0.23g, 1mol%), return stirring 8 hours.After reaction, dimethylbenzene is concentrated under reduced pressure, the mixture of concentration is dissolved in the chlorine of 400mL In imitative, it is washed with water 2 times.Organic layer is separated, anhydrous magnesium sulfate is added, is filtered after stirring, is evaporated under reduced pressure filtrate.By the change of concentration Close object purified by silica gel column chromatography, thus manufactured compound 1 (23.4g, yield 74%, MS:[M+H]+=720).
Production Example 5
The manufacture of step 1) compound 2-1
Using intermediate B, tested by method identical with the Production Example of compound 1-1, to manufacture chemical combination Object 2-1.
The manufacture of step 2) compound 2
Using compound 2-1, tested by method identical with the Production Example of compound 1, to manufacture chemical combination Object 2.(MS:[M+H]+=644)
Production Example 6
The manufacture of step 1) compound 3-1
Using 4- bromaniline (25g, 145mmol) and dibenzo [b, d] furans -4- ylboronic acid (30.8g, 145mmol), lead to It crosses method identical with the Production Example of compound 1-2 to be tested, to manufacture compound 3-1 (25.6g, 68%).
The manufacture of step 2) compound 3-2
Using compound 3-1 (20g, 77mmol) and intermediate C (24.6g, 77mmol), pass through the manufacture with compound 1 The identical method of example is tested, to manufacture compound 3-2 (30.5g, 73%).
The manufacture of step 3) compound 3
Using bromo- 9, the 9- dimethyl -9H- fluorenes (9.1g, 33mmol) of compound 3-2 (18g, 33mmol) and compound 4-, It is tested by method identical with the Production Example of compound 1-1, to manufacture compound 3 (18.3g, 75%, MS:[M+ H]+=734).