CN108250189A - Novel heterocyclic compounds and utilize its organic illuminating element - Google Patents

Novel heterocyclic compounds and utilize its organic illuminating element Download PDF

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CN108250189A
CN108250189A CN201711418325.1A CN201711418325A CN108250189A CN 108250189 A CN108250189 A CN 108250189A CN 201711418325 A CN201711418325 A CN 201711418325A CN 108250189 A CN108250189 A CN 108250189A
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CN108250189B (en
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李征夏
许东旭
李东勋
郑珉祐
李周泳
蔡美荣
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LG Corp
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Abstract

The present invention provides new compound and utilizes its organic illuminating element.Above compound represents by following chemical formula 1, wherein, X O, S or SiR5R6, R1aTo R4aIt is each independently L1‑HAr1Or A1, R1aTo R4aAt least one of it is above be L1‑HAr1, R1bTo R4bIt is each independently L2‑HAr2Or A2, R1bTo R4bAt least one of it is above be L2‑HAr2.[chemical formula 1]

Description

Novel heterocyclic compounds and utilize its organic illuminating element
Technical field
The present invention relates to a kind of novel heterocyclic compounds and the organic illuminating elements for including it.
Background technology
In general, organic light emission phenomenon refers to, the phenomenon that electric energy being made to be changed into luminous energy using organic substance.Using organic The organic illuminating element of luminescence phenomenon has wide viewing angle, excellent contrast, fast response time, brightness, driving voltage and sound Answer speed characteristics excellent, so as to largely be 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 of organic illuminating element and stability, often by utilizing the multilayer knot that respectively different substance is formed Above-mentioned organic matter layer is configured to, for example, can be noted by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electronics Enter the formation such as layer.For the structure of such organic illuminating element, if applying voltage between electrodes, hole from Anode is injected into organic matter layer, and electronics is injected into organic matter layer from cathode, is formed when institute's injected holes and electronics meet sharp Sub (exciton), will send out light when which transits to ground state again.
For the organic matter used in organic illuminating element as described above, lasting requirement exploitation new material.
Existing technical literature
Patent document
Patent document 1：Korean Patent Publication No. 10-2000-0051826
Invention content
The present invention relates to novel heterocyclic compounds and include its organic illuminating element.
The present invention provides a kind of compound represented by following chemical formula 1：
[chemical formula 1]
In above-mentioned chemical formula 1,
X is O, S or SiR5R6,
R1aTo R4aIt is each independently L1-HAr1Or A1, R1aTo R4aAt least one of it is above be L1-HAr1,
R1bTo R4bIt is each independently L2-HAr2Or A2, R1bTo R4bAt least one of it is above be L2-HAr2,
R1aFor L1-HAr1When, R1bIt is not L2-HAr2,
R2aFor L1-HAr1When, R2bIt is not L2-HAr2,
R3aFor L1-HAr1When, R3bIt is not L2-HAr2,
R4aFor L1-HAr1When, R4bIt is not L2-HAr2,
L1And L2It is each independently Direct Bonding, substituted or unsubstituted C6-60Arlydene or substituted or unsubstituted Include the more than one heteroatomic C in O, N, Si and S2-60Heteroarylidene, but do not include substituted or unsubstituted Asia Carbazyl,
HAr1And HAr2It is each independently any one in following radicals, and comprising N more than at least two,
X1To X3It is each independently N or CR7,
A1、A2、R5To R7、R11And R12It is each independently hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-60 Alkyl, substituted or unsubstituted C1-60Halogenated alkyl, substituted or unsubstituted C1-60Alkoxy, substituted or unsubstituted C1-60Halogen For alkoxy, substituted or unsubstituted C3-60Cycloalkyl, substituted or unsubstituted C2-60Alkenyl, substituted or unsubstituted C6-60Virtue Base, substituted or unsubstituted C6-60Aryloxy group or substituted or unsubstituted comprising more than one miscellaneous in N, O and S The C of atom2-60Heterocycle,
N1 is 0 to 3 integer.
Preferably, R1aFor L1-HAr1、R2bFor L2-HAr2Or R2aFor L1-HAr1、R1bFor L2-HAr2When, HAr1And HAr2 In do not include
In addition, the present invention provides a kind of organic illuminating element comprising 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 of compound contained above represented by above-mentioned chemical formula 1 in above-mentioned organic matter layer.
The above-mentioned compound represented by chemical formula 1 can make as the material of the organic matter layer of organic illuminating element With can realize the raising of the raising of efficiency, low driving voltage and/or life characteristic in organic illuminating element.Particularly, by The compound that above-mentioned chemical formula 1 represents can be used as the material of luminescent layer.
Description of the drawings
Fig. 1 illustrates the examples of 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 formed.
Fig. 3 to Fig. 5 represents the PL of compound according to the present inventionmaxData.
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
Specific embodiment
In the following, in order to help to understand the present invention, it is illustrated in more details.
In this specification,OrRepresent the key being connect with other substituent groups, singly-bound is represented by L1And L2The part of expression There is no the situations of other atoms.
In this specification, " substituted or unsubstituted " this term refers to, by selected from deuterium, halogen group, cyano, nitro, Hydroxyl, carbonyl, ester group, imide, amino, oxidation phosphino-, alkoxy, aryloxy group, alkyl sulfenyl ( Alkyl thioxy), alkyl sulfenyl ( Aryl thioxy), alkyl sulfoxide base ( Alkyl sulfoxy), aryl sulfoxid es base (Aryl sulfoxy), silicyl, boryl, alkyl, ring Alkyl, alkenyl, aryl, aralkyl, arylalkenyl, alkylaryl, alkyl amine group, aralkyl amido, heteroaryl amido, arylamine Base, aryl phosphino- replace comprising more than one substituent group in the more than one heterocycle in N, O and S atom or do not take Generation or the substituent group being formed by connecting by the substituent group of 2 or more in foregoing illustrative substituent group replace or unsubstituted.Example Such as, " substituent group that the substituent group of 2 or more is formed by connecting " can be xenyl.That is, xenyl can be aryl, can also solve It is interpreted as 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, Can be the compound of following structure, but it's not limited to that.
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 substitution of carbon atom number 6 to 25.Specifically, can be the compound of following structural formula, but it's not limited to that.
In this specification, the carbon atom number of imide is not particularly limited, but preferably carbon atom number is 1 to 25.Specifically For, can be the compound of following structure, but it's not limited to that.
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 it's not limited to that.
In this specification, boryl specifically has trimethyl boryl, triethyl group boryl, fert-butyidimethylsilyl boryl, triphenyl borine Base, phenyl boryl etc., but it's not limited to that.
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 branch 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, tertiary butyl, sec-butyl, 1- methyl-butvls, 1- second Base-butyl, amyl, n-pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, n-hexyl, 1- methyl amyls, 2- methyl amyls, 4- Methyl -2- amyls, 3,3- dimethylbutyls, 2- ethyl-butyls, heptyl, n-heptyl, 1- methylhexyls, cyclopentyl-methyl, hexamethylene Ylmethyl, octyl group, n-octyl, t-octyl, 1- methylheptyls, 2- ethylhexyls, 2- propylpentyls, n-nonyl, 2,2- dimethyl Heptyl, 1- Ethyl-propyls, 1,1- Dimethyl-propyls, isohesyl, 2- methyl amyls, 4- methylhexyls, 5- methylhexyls etc., but It's not limited to that.
In this specification, above-mentioned alkenyl can be linear chain or branch 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- cyclobutenyls, 2- cyclobutenyls, 3- cyclobutenyls, 1- pentenyls, 2- pentenyls, 3- pentenyls, 3- methyl-1s- Cyclobutenyl, 1,3- butadiene, pi-allyl, 1- phenylethylene -1- bases, 2- phenylethylene -1- bases, 2,2- diphenylethlene -1- bases, Bis- (hexichol -1- bases) ethylene -1- bases of 2- phenyl -2- (naphthalene -1- bases) ethylene -1- bases, 2,2-,Base, styryl etc., but not It is defined in this.
In this specification, cycloalkyl is not particularly limited, but the preferably cycloalkyl of carbon atom number 3 to 60, real according to one Mode is applied, the carbon atom number of above-mentioned cycloalkyl is 3 to 30.According to another embodiment, the carbon atom number of above-mentioned cycloalkyl for 3 to 20.According to another embodiment, the carbon atom number of above-mentioned cycloalkyl is 3 to 6.Specifically, there are cyclopropyl, cyclobutyl, ring penta Base, 3- methylcyclopentyls, 2,3- dimethylcyclopentyls, cyclohexyl, 3- methylcyclohexyls, 4- methylcyclohexyls, 2,3- dimethyl Cyclohexyl, 3,4,5- trimethylcyclohexyls, 4- tert-butylcyclohexyls, suberyl, cyclooctyl etc., but it's not limited to that.
In this specification, aryl is not particularly limited, but the preferably aryl of carbon atom number 6 to 60, can be monocyclic 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.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 be naphthalene, anthryl, phenanthryl, pyrenyl, base,Base, fluorenyl etc., but not It is defined in 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 case of base is substituted, Ke Yiwei
Deng.But simultaneously It is not limited to this.
In this specification, heterocycle is as heteroatomic heterocycle, carbon atom comprising more than one in O, N, Si and S 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, pyridyl group, bipyridyl, pyrimidine radicals, triazine radical, acridinyl, is rattled away at triazolyl Piperazine base, pyrazinyl, quinolyl, quinazolyl, quinoxalinyl, phthalazinyl, Pyridopyrimidine base, pyrido-pyrazine base, pyrazine are simultaneously Pyrazinyl, isoquinolyl, indyl, carbazyl, benzoOxazolyl, benzimidazolyl, benzothiazolyl, benzo carbazole base, benzene It is bithiophene base, dibenzothiophene, benzofuranyl, phenanthroline (phenanthroline), differentOxazolyl, thiadiazolyl group, Phenothiazinyl and dibenzofuran group etc., it is not limited to this.
In this specification, the illustration phase of aryl and above-mentioned aryl in aralkyl, arylalkenyl, alkylaryl, arylamine group Together.In this specification, the alkyl in aralkyl, alkylaryl, alkyl amine group is identical with the illustration of abovementioned alkyl.This specification In, the heteroaryl in heteroaryl amine can be applicable in the above-mentioned explanation about heterocycle.In this specification, alkenyl in arylalkenyl with The illustration of above-mentioned alkenyl is identical.In this specification, arlydene is divalent group, in addition to this, can be applicable in above-mentioned about aryl Explanation.In this specification, heteroarylidene is divalent group, in addition to this, can be applicable in the above-mentioned explanation about heterocycle.This theory In bright book, hydrocarbon ring is not 1 valency group, and is that 2 substituent groups are combined into, and in addition to this, can be applicable in above-mentioned about aryl Or the explanation of cycloalkyl.In this specification, heterocycle is not 1 valency group, and is that 2 substituent groups are combined into, in addition to this, can To be applicable in the above-mentioned explanation about heterocycle.
In addition, the present invention provides a kind of compound represented by above-mentioned chemical formula 1.
In above-mentioned chemical formula 1, X can be O, S, Si (CH3)2Or Si (C6H5)2.Or X can be O.
In addition,
R1aTo R4aIn one be L1-HAr1, remaining can be A1,
R1bTo R4bIn one be L2-HAr2, remaining can be A2。
For example,
R1aFor L1-HAr1, R2bFor L2-HAr2；
R1aFor L1-HAr1, R3bFor L2-HAr2；
R1aFor L1-HAr1, R4bFor L2-HAr2；
R2aFor L1-HAr1, R3bFor L2-HAr2；
R2aFor L1-HAr1, R4bFor L2-HAr2；Or
R3aFor L1-HAr1, R4bFor L2-HAr2。
In addition, L1And L2Direct Bonding or substituted or unsubstituted C can be each independently6-60Arlydene.
In addition, L1And L2Direct Bonding or any one in following radicals can be each independently：
Specifically, for example, L1And L2Direct Bonding or any in following radicals can be each independently It is a：
In addition, L1And L2At least one of can be Direct Bonding.For example, L1Can be Direct Bonding, L2Can be straight Meet bonding or L1And L2It can be Direct Bonding.
In addition, HAr1And HAr2Any one in following radicals can be each independently：
In above-mentioned group,
R7、R11And R12It is each independently hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-20Alkyl, substitution Or unsubstituted C1-20Halogenated alkyl, substituted or unsubstituted C6-20Aryl or substituted or unsubstituted include are selected from N, O and S In more than one heteroatomic C2-20Heterocycle.
In addition, HAr1And HAr2Any one in following radicals can be each independently：
In above-mentioned group,
R11And R12It is each independently hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-20Alkyl, substitution or Unsubstituted C1-20Halogenated alkyl, substituted or unsubstituted C6-20Aryl or it is substituted or unsubstituted include in N, O and S More than one heteroatomic C2-20Heterocycle.
But R1aFor L1-HAr1、R2bFor L2-HAr2Or R2aFor L1-HAr1、R1bFor L2-HAr2When, HAr1And HAr2In Do not include
In R1aFor L1-HAr1、R2bFor L2-HAr2Or R2aFor L1-HAr1、R1bFor L2-HAr2Compound in, include quilt HAr1And HAr2During substituted or unsubstituted triazine radical, compared with the organic illuminating element of application compound according to the present invention, Electronics is opposite to be not easy to be injected, therefore the balance between hole and electronics is destroyed and driving voltage height and efficiency reduction.
For example, L1-HAr1And L2-HAr2Any one in following radicals can be each independently：
In addition, A1And A2Hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C can be each independently1-20Alkane Base, substituted or unsubstituted C1-20Halogenated alkyl or substituted or unsubstituted C6-20Aryl.
For example, A1And A2Can be hydrogen.
At this moment, n1 represents R11Number, n1 be more than 2 when, the R of 2 or more11It can be the same or different from each other.
In addition, above compound can be any one in the compound represented by following chemical formula 1-1 to 1-6：
[chemical formula 1-1]
[chemical formula 1-2]
[chemical formula 1-3]
[chemical formula 1-4]
[chemical formula 1-5]
[chemical formula 1-6]
In above-mentioned chemical formula 1-1 to 1-6,
For X, L1、L2、HAr1And HAr2Explanation it is identical with the definition in above-mentioned chemical formula 1.
In addition, above compound can be any one in following compounds：
The compound represented by above-mentioned chemical formula 1 has asymmetricly to be connected with relative to nuclear structures such as dibenzofurans L1-HAr1And L2-HAr2The structure of substituent group, so as to have high efficiency, low driving electricity using its organic illuminating element Pressure, high brightness and long-life etc..
It on the other hand, can be by such as by the compound that above-mentioned chemical formula 1-1 to 1-6 is represented respectively as an example The manufacturing method manufacture of following reaction equations 1 to 6.Above-mentioned manufacturing method can will embody in aftermentioned Production Example.
[reaction equation 1]
[reaction equation 2]
[reaction equation 3]
[reaction equation 4]
[reaction equation 5]
[reaction equation 6]
In above-mentioned reaction equation 1 to 6, for L1、L2、HAr1And HAr2Explanation it is identical with the definition in above-mentioned chemical formula 1.
The compound represented by above-mentioned chemical formula 1 can refer to above-mentioned reaction equation 1 to 6, according to the compound to be manufactured Structure, suitably replace initial substance and manufacture.
In addition, present invention offer is a kind of to include the organic illuminating element of compound represented by above-mentioned chemical formula 1.As one A example, the present invention a kind of organic illuminating element is provided comprising：It is first electrode, opposed with above-mentioned first electrode and have Second electrode and have 1 layer or more of organic matter layer between above-mentioned first electrode and above-mentioned second electrode, it is above-mentioned organic 1 layer of compound contained above represented by above-mentioned chemical formula 1 in nitride layer.
The organic matter layer of organic illuminating element of the present 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, the organic illuminating element of the present invention, which can have, includes 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, can include less organic layer.
For example, above-mentioned organic matter layer can include luminescent layer, above-mentioned luminescent layer can include what is represented by above-mentioned chemical formula 1 Compound.Specifically, the compound represented by above-mentioned chemical formula 1 can be used as material of main part and comprising.
Particularly, compound according to the present invention has PL maximums compared with the material of main part compound used in the past The characteristics of peak (PL peak max) is shorter wavelength, HOMO energy levels height and band gap bigger.
At this moment, above-mentioned luminescent layer can also include the dopant compound for sending out phosphorescence.Workable phosphorescent dopants material Material is as described later, but it's not limited to that.
In addition, above-mentioned organic matter layer can include above-mentioned electron transfer layer, electron injecting layer or be carried out at the same time electron-transport With the layer of electron injection, above-mentioned electron transfer layer, electron injecting layer or be carried out at the same time the layer of electron-transport and electron injection can be with Include the compound represented by above-mentioned chemical formula 1.
The organic matter layer of organic illuminating element of the present 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, the organic illuminating element of the present invention can also have other than luminescent layer Comprising the hole injection layer between above-mentioned first electrode and above-mentioned luminescent 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, can include less or more layer of organic layer.
In addition, organic illuminating element according to the present invention can be sequentially laminated on substrate anode, 1 layer or more The organic illuminating element of the structure of organic matter layer and cathode (standard type (normal type)).It is in addition, according to the present invention Organic illuminating element can be the reverse structure that cathode, 1 layer or more of organic matter layer and anode are sequentially laminated on substrate The organic illuminating element of (inversion type (inverted type)).For example, the organic light emission member involved by one embodiment of the invention The structure of part is illustrated in Fig. 1 and Fig. 2.
Fig. 1 illustrates the examples of organic illuminating element being made of substrate 1, anode 2, luminescent layer 3, cathode 4.In this knot In structure, the compound represented by above-mentioned chemical formula 1 may be embodied in above-mentioned luminescent layer.
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 formed.In this configuration, the compound represented by above-mentioned chemical formula 1 can include In 1 layer or more in above-mentioned hole injection layer, hole transmission layer, luminescent layer and electron transfer layer.
About organic illuminating element according to the present invention, 1 layer in above-mentioned organic matter layer is contained above by above-mentioned chemistry The compound that formula 1 represents, in addition to this, can be manufactured by material well known in the art and method.In addition, above-mentioned organic In the case that light-emitting component includes multiple organic matter layers, above-mentioned organic matter layer can be by identical substance or different substance shapes Into.
For example, organic illuminating element according to the present invention can be by stacking gradually first electrode, organic on substrate Nitride layer and second electrode and manufacture.At this moment, it can manufacture as follows：Utilize sputtering (sputtering) or electron-beam vapor deposition method (e- Beam evaporation) etc PVD (physical vapor deposition method, physical Vapor Deposition) method, in substrate Upper evaporation metal or conductive metal oxide or their alloy and form anode, then on the anode formed packet Then organic matter layer containing hole injection layer, hole transmission layer, luminescent layer and electron transfer layer is deposited available on organic matter layer Make 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, about the compound that above-mentioned chemical formula 1 represents, when manufacturing organic illuminating element, can not only utilize true Empty vapour deposition method can also form organic matter layer using solution coating method.Here, 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.
Other than this method, can also on substrate successively evaporation cathode substance, organic matter layer, anode material and make Make organic illuminating element (WO 2003/012890).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 hole is enable successfully to be injected 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- dioxies) 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 made easily to be injected 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 Close object：Have the ability of transporting holes, there is the hole injection effect from anode, for the excellent of luminescent layer or luminescent material Hole injection effect, generated exciton is prevented in luminescent layer to be migrated 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 substance that the mobility in hole is big is suitable.As concrete example, there are aryl amine system organic matter, electroconductive polymer, Yi Jitong When there are block copolymer of conjugate moiety and non-conjugated portion etc., it is not limited to this.
It is that can receive hole and electronics respectively from hole transmission layer and electron transfer layer and make as above-mentioned luminescent substance They with reference to and send out the substance of the light of visible light region, preferably for the high substance of the quantum efficiency of fluorescence or phosphorescence.As Concrete example has 8- Hydroxy-quinolin aluminum complexes (Alq3)；Carbazole based compound；Two polystyrene-based (dimerized Styryl) compound；BAlq；10- hydroxy benzo quinoline metal compounds；BenzoAzoles, benzothiazole and benzimidazole system Close object；Poly- (to phenylenevinylenes) (PPV) is macromolecule；Loop coil (spiro) compound；Polyfluorene, rubrene etc., but simultaneously not only It is limited to this.
As described above, above-mentioned luminescent layer can include material of main part and dopant material.
As dopant material, have aromatic amine derivative, styrylamine compounds, boron complexes, fluoranthene compound, Metal complex etc..It is the aromatic series with substituted or unsubstituted arylamino specifically, as aromatic amine derivative Fused-ring derivatives, have the pyrene with arylamino, anthracene,Two indeno pyrenes (Periflanthene) etc., as styryl amine Compound is that substitution has the compound of at least one aryl vinyl on substituted or unsubstituted arylamine, by selected from aryl, One or more substituent group substitution or unsubstituted in silicyl, alkyl, cycloalkyl and arylamino.It is specific and Speech, has styryl amine, styryl diamines, styryl triamine, styryl tetramine etc., but it's not limited to that.In addition, As metal complex, there are complex of iridium, platinum complex etc., but it's not limited to that.
Above-mentioned electron transfer layer is to receive electronics and by the layer of electron-transport to luminescent layer from electron injecting layer, as electronics Transport materials are can to receive electronics well from cathode and transfer them to the substance of luminescent layer, big to the mobility of electronics Substance be suitable.As concrete example, there are the Al complexs of 8-hydroxyquinoline, comprising Alq3Complex, organic free radical Compound, hydroxyl brass-metal complex etc., it is not limited to this.Electron transfer layer can be as used in the prior art As be used together with the cathode substance of any desired.Particularly, the example of suitable cathode substance is with low work function And with aluminium layer or the common substance of silver layer.Specifically, have caesium, barium, calcium, ytterbium and samarium, in the case of each substance, and aluminium Layer or silver layer accompany.
Above-mentioned electron injecting layer be injection come self-electrode electronics layer, preferably following compound：With transmission electronics Ability, have the electron injection effect from cathode, the excellent electron injection effect for 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 5 membered ring derivatives etc., but simultaneously It is not limited to this.
As above-mentioned metal complex, have 8-hydroxyquinoline lithium, bis- (8-hydroxyquinoline) zinc, bis- (8-hydroxyquinoline) copper, It is bis- (8-hydroxyquinoline) manganese, three (8-hydroxyquinoline) aluminium, three (2- methyl -8-hydroxyquinoline) aluminium, three (8-hydroxyquinoline) galliums, double (10- hydroxy benzos [h] quinoline) beryllium, bis- (10- hydroxy benzos [h] quinoline) zinc, bis- (2- methyl -8- quinoline) gallium chlorides, bis- (2- Methyl -8- quinoline) (o-cresol) gallium, bis- (2- methyl -8- quinoline) (1- naphthols) aluminium, bis- (2- methyl -8- quinoline) (beta naphthals) Gallium etc., but it's not limited to that.
The organic illuminating element of the present invention can be top emission type, bottom emission type or double according to used material To light emitting-type.
In addition, the compound represented 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.
The compound represented by above-mentioned chemical formula 1 and the manufacture comprising its organic illuminating element have in the examples below Illustrate to body.But following embodiments are illustrative for 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 1
1) manufacture of intermediate 1-1d
(A) manufacture of intermediate 1-1a
Under nitrogen atmosphere, in the round-bottomed flask of 2000mL, by 2- bromines resorcinol (50g, 0.26mol) and the chloro- 2- of 3- After flurophenyl boronic acid (46.1g, 0.21mol) is dissolved in tetrahydrofuran (500mL), 1.5M wet chemicals (400mL) are added, are added After entering bis- (tri-tert-butylphosphine) palladiums (0) (1.35g, 2.36mmol), heating stirring 1 hour.Cool the temperature to room temperature, separation removal Water layer is concentrated under reduced pressure after being dried with anhydrous magnesium sulfate, dry after being recrystallized using hexane, so as to produce above-mentioned intermediate 1- 1a (49.8g, yield 79%, MS:[M+H]+=239).
(B) manufacture of intermediate 1-1b
In the round-bottomed flask of 500mL, by intermediate 1-1a (49.8g, 0.21mol) and calcium carbonate (57.7g, After 0.42mol) being dissolved in n-methyl-2-pyrrolidone (200mL), heating stirring 2 hours.Room temperature is cooled the temperature to, it is inverse in water It precipitates and filters.It after being completely dissolved in dichloromethane, is washed with water, after being dried with anhydrous magnesium sulfate, is concentrated under reduced pressure, utilizes ethyl alcohol It is dry after recrystallization, so as to produce above-mentioned intermediate 1-1b (31.8g, yield 70%, MS:[M+H]+=219).
(C) manufacture of intermediate 1-1c
In the round-bottomed flask of 500mL, intermediate 1-1b (31.8g, 0.15mol) is dissolved in acetonitrile (150mL), by carbon Sour calcium (33.1g, 0.24mol) be dissolved in water (150mL) and after adding in, be slowly added dropwise at 0 DEG C nine fluorine butane sulfuryl fluorides (28.7mL, 0.16mol) 30 minutes.Then, it has been stirred at room temperature 3 hours.It is filtered after the reaction was complete, after being completely dissolved in dichloromethane, It is washed with water, after being dried with anhydrous magnesium sulfate, is concentrated under reduced pressure, it is dry after being recrystallized using ethyl alcohol, so as to produce above-mentioned centre Body 1-1c (53.3g, yield 73%, MS:[M+H]+=501).
(D) manufacture of intermediate 1-1d
By intermediate 1-1c (53.3g, 0.11mol), 4,4,5,5- tetramethyls-[1,3,2]-dioxaborinate (28.4g, 17.85mol)、Pd(dppf)Cl2(0.78g, 1.06mmol), KOAc (31.3g, 0.32mol) are added to twoAlkane (650mL), It has stirred under reflux conditions 8 hours.Room temperature is cooled the temperature to, solvent is concentrated under reduced pressure.The concentrate is completely dissolved in CHCl3Afterwards, it is washed with water, the solution for being dissolved with product is concentrated under reduced pressure, is purified using column chromatography, so as to obtain Intermediate 1-1d (30.1g, yield 86%, MS:[M+H]+=329).
2) compound synthesis of intermediate 1-1f
(A) manufacture of intermediate 1-1e
Under nitrogen atmosphere, in the round-bottomed flask of 500mL, by intermediate 1-1d (30.1g, 91.6mmol) and 2- chloro- 4, After 6- diphenylpyrimidins (1a, 24.4g, 91.6mmol) are dissolved in tetrahydrofuran (200mL), the wet chemical of 1.5M is added (100mL), after adding in tetrakis triphenylphosphine palladium (1.06g, 0.92mmol), heating stirring 11 hours.Room temperature is cooled the temperature to, point It leaves away except water layer, after being dried with anhydrous magnesium sulfate, is concentrated under reduced pressure, it is dry after being recrystallized using dichloro-benzenes, it is above-mentioned so as to produce Intermediate 1-1e (32.1g, yield 81%, MS:[M+H]+=433).
(B) manufacture of intermediate 1-1f
By intermediate 1-1e (32.1g, 74.1mmol), 4,4,5,5- tetramethyls-[1,3,2]-dioxaborinate (19.8g, 77.9mmol)、Pd(dba)2(1.28g,2.22mmol)、PCy3(1.25g, 4.45mmol), KOAc (21.8g, 0.22mol) add Enter to twoIn alkane (400mL), stir under reflux conditions 13 hours.Room temperature is cooled the temperature to, solvent depressurize dense Contracting.The concentrate is completely dissolved in CH Cl3Afterwards, it is washed with water, the solution for being dissolved with product is concentrated under reduced pressure, utilize After ethyl alcohol recrystallization, dry and purifying, so as to obtain intermediate 1-1f (29.5g, yield 76%, MS:[M+H]+=525).
3) synthesis of compound 1
Under nitrogen atmosphere, in 500mL round-bottomed flasks, by intermediate 1-1f (15g, 28.6mmol), 4- ([1,1'- biphenyl Base] -4- bases) after -2- chloro-6-phenyls pyridine (1b, 9.81g, 28.6mmol) is dissolved in tetrahydrofuran (150mL), add 1.5M's Wet chemical (70mL), after adding in bis- (tri-tert-butylphosphine) palladiums (0) (0.15g, 0.29mmol), heating stirring 9 hours.It will Temperature is down to room temperature, and filtering is washed with water and removes alkali (base).It is recrystallized using n-methyl-2-pyrrolidone, so as to obtain Above compound 1 (13.4g, yield 66%, MS:[M+H]+=705).
Production Example 2：The synthesis of compound 2
Using 2- (4- bromophenyls) -4,6- hexichol yl pyridines (1c) instead of intermediate 1b, in addition to this, by with manufactureization The method that the method for conjunction object 1 is identical has manufactured above compound 2c (8.9g, yield 69%, MS:[M+H]+=705).
Production Example 3：The synthesis of compound 3
1) compound synthesis of intermediate 1-1h
(A) manufacture of intermediate 1-1g
Intermediate 1a is replaced using intermediate 1c, in addition to this, passes through the side identical with the method for manufacturing intermediate 1-1e Method has manufactured above-mentioned intermediate 1-1g (10.5g, yield 71%, MS:[M+H]+=509).
(B) manufacture of intermediate 1-1h
Intermediate 1-1e is replaced using intermediate 1-1g, in addition to this, by identical with the method for manufacturing intermediate 1-1f Method manufactured above-mentioned intermediate 1-1h (9.1g, yield 71%, MS:[M+H]+=601).
2) synthesis of compound 3
Using intermediate 1-1h and intermediate 1a replace intermediate 1-1f close intermediate 1b, in addition to this, by with manufacture The method that the method for compound 1 is identical has manufactured above compound 3 (7.8g, yield 73%, MS:[M+H]+=705).
Production Example 4：The manufacture of compound 4
1) compound synthesis of intermediate 2-1b
(A) manufacture of intermediate 2-1a
Under nitrogen atmosphere, in the round-bottomed flask of 1000mL, 4- chlorodiphenyls and furans (75g, 0.37mol) are dissolved in DMF After (700mL), after 0 DEG C of point of 5 addition NBS (69.2g, 0.39mol), it is stirred at room temperature 3 hours.Then, solution is carried out After decompression, ethyl acetate is dissolved in, after being washed with water, organic layer is detached and depressurizes and completely eliminated solvent.It is obtained using column chromatography Intermediate 2-1a (92.5g, yield 89%, MS are arrived:[M+H]+=280).
(B) manufacture of intermediate 2-1b
By intermediate 2-1a (92.5g, 0.33mol), 4,4,5,5- tetramethyls-[1,3,2]-dioxaborinate (87.9g, 0.35mol)、Pd(dppf)Cl2(2.41g, 3.30mmol), KOAc (97.1g, 0.99mol) are added to twoAlkane (1000mL) In, it has stirred under reflux conditions 9 hours.Room temperature is cooled the temperature to, solvent is concentrated under reduced pressure.The concentrate is completely molten In CHCl3Afterwards, it is washed with water, the solution for being dissolved with product is concentrated under reduced pressure, it is dry and pure after being recrystallized using ethyl alcohol Change, so as to obtain intermediate 2-1b (115g, yield 67%, MS:[M+H]+=329).
2) compound synthesis of intermediate 2-1d
(A) manufacture of intermediate 2-1c
Intermediate 1-1d is replaced using intermediate 2-1b, in addition to this, by identical with the method for manufacturing intermediate 1-1e Method manufactured above-mentioned intermediate 2-1c (38.5g, yield 73%, MS:[M+H]+=434).
(B) manufacture of intermediate 2-1d
Intermediate 1-1e is replaced using intermediate 2-1c, in addition to this, by identical with the method for manufacturing intermediate 1-1f Method manufactured above-mentioned intermediate 2-1d (30.8g, yield 66%, MS:[M+H]+=525).
3) synthesis of compound 4
Intermediate 1-1f is replaced, and use 2- ([1,1'- xenyl] -3- bases) chloro- 6- benzene of -4- using intermediate 2-1d Base -1,3,5-triazines (2a) in addition to this, is manufactured instead of intermediate 1b by the method identical with the method for manufacturing compound 1 Above compound 4 (32.9g, yield 79%, MS:[M+H]+=706).
Production Example 5：The manufacture of compound 5
1) compound synthesis of intermediate 2-2b
(A) manufacture of intermediate 2-2a
Using chloro- 4, the 6- diphenyl of 2- -1,3,5-triazines (2b) instead of intermediate 1a, in addition to this, by in manufacture The method that the method for mesosome 2-1c is identical has manufactured above-mentioned intermediate 2-2a (40.2g, yield 76%, MS:[M+H]+=434).
(B) manufacture of intermediate 2-2b
Intermediate 2-1c is replaced using intermediate 2-2a, in addition to this, by identical with the method for manufacturing intermediate 2-1d Method manufactured above-mentioned intermediate 2-2b (34.1g, yield 70%, MS:[M+H]+=526).
2) synthesis of compound 5
Intermediate 2-1d is replaced, and use 2- chloro- 4- (dibenzo [b, d] furans -1- bases) -6- using intermediate 2-2b Phenyl -1,3,5-triazines (2c) in addition to this, passes through the method system identical with the method for manufacturing compound 3 instead of intermediate 2a Above compound 5 (11.6g, yield 74%, MS are made:[M+H]+=721).
Production Example 6：The manufacture of compound 6
Intermediate 2-1d is replaced, and use 2- (3- bromophenyls) -4,6- diphenyl -1,3,5- tri- using intermediate 2-2b Piperazine (2d) in addition to this, above compound has been manufactured by the method identical with the method for manufacturing compound 3 instead of intermediate 2a 6 (9.0g, yield 70%, MS:[M+H]+=707).
Production Example 7：The manufacture of compound 7
Intermediate 2-1d is replaced, and use 4- ([1,1'- xenyl] -4- bases) -6- (4- chlorobenzenes using intermediate 2-2b Base) -2- phenylpyridines (2f) are instead of intermediate 2a, and in addition to this, pass through the method identical with the method for manufacturing compound 3 and manufacture Above compound 7 (11.3g, yield 71%, MS:[M+H]+=782).
Production Example 8：The manufacture of compound 8
1) compound synthesis of intermediate 2-3b
(A) manufacture of intermediate 2-3a
Intermediate 1a is replaced using intermediate 2d, in addition to this, passes through the side identical with the method for manufacturing intermediate 2-1c Method has manufactured above-mentioned intermediate 2-3a (38.1g, yield 71%, MS:[M+H]+=510).
(B) manufacture of intermediate 2-3b
Intermediate 2-1c is replaced using intermediate 2-3a, in addition to this, by identical with the method for manufacturing intermediate 2-1d Method manufactured above-mentioned intermediate 2-3b (29.3g, yield 65%, MS:[M+H]+=602).
2) synthesis of compound 8
Intermediate 2-1d is replaced, and intermediate 2a is replaced using intermediate 2b using intermediate 2-3b, in addition to this, led to It crosses the method identical with the method for manufacturing compound 3 and has manufactured above compound 8 (24.4g, yield 70%, MS:[M+H]+= 707)。
Production Example 9：The manufacture of compound 9
1) compound synthesis of intermediate 3-1d
(A) manufacture of intermediate 3-1a
Using 2- iodobenzenes -1,3- glycol (50g, 0.21mol) instead of 2- bromine resorcinols, in addition to this, by with manufacture The method that the method for intermediate 1-1a is identical has manufactured above-mentioned intermediate 3-1a (38.9g, yield 77%, MS:[M+H]+= 239)。
(B) manufacture of intermediate 3-1b
Intermediate 1-1a is replaced using intermediate 3-1a, in addition to this, by identical with the method for manufacturing intermediate 1-1b Method manufactured above-mentioned intermediate 3-1b (24.3g, yield 68%, MS:[M+H]+=219).
(C) manufacture of intermediate 3-1c
Intermediate 1-1b is replaced using intermediate 3-1b, in addition to this, by identical with the method for manufacturing intermediate 1-1c Method manufactured above-mentioned intermediate 3-1c (37.8g, yield 74%, MS:[M+H]+=500).
(D) manufacture of intermediate 3-1d
Intermediate 1-1c is replaced using intermediate 3-1c, in addition to this, by identical with the method for manufacturing intermediate 1-1d Method manufactured above-mentioned intermediate 3-1d (8.1g, yield 88%, MS:[M+H]+=329).
2) compound synthesis of intermediate 3-1f
(A) manufacture of intermediate 3-1e
Intermediate 1-1d is replaced, and intermediate 1a is replaced using intermediate 2b using intermediate 3-1d, in addition to this, led to It crosses the method identical with the method for manufacturing intermediate 1-1e and has manufactured above-mentioned intermediate 3-1e (9.3g, yield 87%, MS:[M+H ]+=434).
(B) manufacture of intermediate 3-1f
Intermediate 1-1e is replaced using intermediate 3-1e, in addition to this, by identical with the method for manufacturing intermediate 1-1f Method manufactured above-mentioned intermediate 3-1f (9.9g, yield 76%, MS:[M+H]+=526).
3) synthesis of compound 9
Intermediate 2-2b is replaced, and use 2- chloro- 4- (dibenzo [b, d] furans -4- bases) -6- using intermediate 3-1f Phenyl -1,3,5-triazines (3a) in addition to this, passes through the method system identical with the method for manufacturing compound 4 instead of intermediate 2c Above compound 9 (6.2g, yield 90.5%, MS are made:[M+H]+=721).
Production Example 10：The manufacture of compound 10
Intermediate 2-2b is replaced, and use 4- ([1,1'- xenyl] -4- bases) -2- chloroquine azoles using intermediate 3-1f Quinoline (3b) in addition to this, above compound has been manufactured by the method identical with the method for manufacturing compound 4 instead of intermediate 2c 10 (4.9g, yield 88%, MS:[M+H]+=680).
Production Example 11：The manufacture of compound 11
(A) manufacture of intermediate 3-2a
By intermediate 3-1c (15.0g, 30.3mmol), 4,4,5,5- tetramethyls-[1,3,2]-dioxaborinate (16.0g, 62.9mmol)、Pd(dba)2(0.52g,0.90mmol)、PCy3(0.5g, 1.80mmol), KOAc (8.82g, 89.9mmol) add Enter to twoIn alkane (200mL), stir under reflux conditions 15 hours.Room temperature is cooled the temperature to, solvent depressurize dense Contracting.Above-mentioned concentrate is completely dissolved in C HCl3Afterwards, it is washed with water, the solution for being dissolved with product is concentrated under reduced pressure, profit After being recrystallized with ethyl alcohol, dry and purifying, so as to obtain intermediate 3-2a (8.3g, yield 65%, MS:[M+H]+=421).
(B) manufacture of compound 7
Under nitrogen atmosphere, in the round-bottomed flask of 250mL, by intermediate 3-2a (8.3g, 19.8mmol), intermediate 2b After (10.6g, 39.5mmol) is dissolved in tetrahydrofuran (100mL), the wet chemical (45mL) of 1.5M is added, adds in bis- (three Tertiary butyl phosphine) after palladium (0) (0.50g, 0.99mmol), heating stirring 6 hours.Cool the temperature to room temperature, filter, be washed with water and Remove alkali (base).It is recrystallized using n-methyl-2-pyrrolidone, so as to obtain above compound 11 (11.6g, yield 93%, MS:[M+H]+=631).
Production Example 12：The manufacture of compound 12
1) compound synthesis of intermediate 3-3b
(A) manufacture of intermediate 3-3a
Using intermediate 3-1c replace intermediate 3-1d, and using 2,4- diphenyl -6- (4- (4,4,5,5- tetramethyls - 1,3,2- dioxaborinate -2- bases) phenyl) -1,3,5-triazines (3b) is instead of intermediate 2b, in addition to this, by in manufacture The method that the method for mesosome 3-1e is identical has manufactured above-mentioned intermediate 3-3a (7.3g, yield 81%, MS:[M+H]+=510).
(B) manufacture of intermediate 3-3b
Intermediate 1-1e is replaced using intermediate 3-3a, in addition to this, by identical with the method for manufacturing intermediate 1-1f Method manufactured above-mentioned intermediate 3-3b (6.7g, yield 77%, MS:[M+H]+=602).
2) synthesis of compound 12
Intermediate 2-3b is replaced using intermediate 3-3b, in addition to this, passes through the side identical with the method for manufacturing compound 5 Method has manufactured above compound 12 (7.2g, yield 91%, MS:[M+H]+=707).
Production Example 13：The manufacture of compound 13
1) compound synthesis of intermediate 3-4b
Intermediate 2b is replaced using intermediate 1a, in addition to this, passes through the side identical with the method for manufacturing intermediate 3-1e After method manufactures above-mentioned intermediate 3-4a, intermediate 3- has then been manufactured by the method identical with the method for manufacturing intermediate 3-1f 4b(9.2g,MS:[M+H]+=525).
2) synthesis of compound 13
Intermediate 2-3b is replaced using intermediate 3-4b, in addition to this, passes through the side identical with the method for manufacturing compound 5 Method has manufactured above compound 13 (8.0g, yield 64%, MS:[M+H]+=706).
Production Example 14：The manufacture of compound 14
(A) manufacture of intermediate 4-1a
Intermediate 2-1b is replaced, and intermediate is replaced using intermediate 3a using dibenzo [b, d] furans -3- ylboronic acids 2b, in addition to this, having manufactured above-mentioned intermediate 4-1a by the method identical with the method for manufacturing intermediate 2-2a, (71.4g is received Rate 88%, MS:[M+H]+=490).
(B) manufacture of intermediate 4-1b
Under nitrogen atmosphere, the mixing that intermediate 4-1a (71.4g, 0.15mol) is dissolved in acetic acid and sulfuric acid (95-96%) is molten Liquid (v:V=5:5) in 1400mL, NBS (28.6g, 0.16mol) is divided 7 times after being slowly added, be stirred at room temperature 3 hours.So Afterwards, water is added in reactant, filters, is washed with water and ethyl alcohol.Using tetrahydrofuran and toluene purifying (recrystallization), so as to obtain Intermediate 4-1b (42.9g, yield 52%, MS are arrived:[M+H]+=568).
(C) manufacture of intermediate 4-1c
Intermediate 3-3a is replaced using intermediate 4-1b, in addition to this, by identical with the method for manufacturing intermediate 3-3b Method manufactured above-mentioned intermediate 4-1c (34.9g, yield 75%, MS:[M+H]+=616).
(D) manufacture of compound 14
Intermediate 2-3b is replaced using intermediate 4-1c, in addition to this, passes through the side identical with the method for manufacturing compound 5 Method has manufactured above compound 14 (30.5g, yield 74%, MS:[M+H]+=721).
Production Example 15：The manufacture of compound 15
(A) manufacture of intermediate 4-2a and 4-2b
Intermediate 2-1b is replaced using dibenzo [b, d] furans -3- ylboronic acids, in addition to this, by with manufacturing intermediate After the identical method of the method for 2-2a manufactures above-mentioned intermediate 4-2a, then by identical with the method for manufacturing intermediate 4-1b Method has manufactured intermediate 4-2b (15.1g, MS:[M+H]+=478).
(B) manufacture of intermediate 4-2c
Intermediate 3-3a is replaced using intermediate 4-2b, in addition to this, by identical with the method for manufacturing intermediate 3-3b Method manufactured above-mentioned intermediate 4-2c (11.8g, yield 71%, MS:[M+H]+=526).
(D) manufacture of compound 15
Intermediate 2-3b is replaced using intermediate 4-2c, in addition to this, passes through the side identical with the method for manufacturing compound 5 Method has manufactured above compound 15 (10.1g, yield 64%, MS:[M+H]+=707).
Production Example 16：The manufacture of compound 16
(A) manufacture of intermediate 4-3a and 4-3b
Intermediate 2-1b is replaced using dibenzo [b, d] furans -3- ylboronic acids, in addition to this, by with manufacturing intermediate After the identical method of the method for 2-2a manufactures above-mentioned intermediate 4-3a, then by identical with the method for manufacturing intermediate 4-1b Method has manufactured intermediate 4-3b (10.7g, MS:[M+H]+=477).
(B) manufacture of intermediate 4-3c
Intermediate 3-3a is replaced using intermediate 4-3b, in addition to this, by identical with the method for manufacturing intermediate 3-3b Method manufactured above-mentioned intermediate 4-3c (8.4g, yield 71%, MS:[M+H]+=525).
(D) manufacture of compound 16
Intermediate 2-3b is replaced using intermediate 4-3c, in addition to this, passes through the side identical with the method for manufacturing compound 5 Method has manufactured above compound 16 (7.6g, yield 67%, MS:[M+H]+=705).
Production Example 17：The manufacture of compound 17
1) compound synthesis of intermediate 5-1d
(A) manufacture of intermediate 5-1a
Use (the chloro- 2- fluorophenyls of 4-) boric acid replace (the chloro- 2- fluorophenyls of 3-) boric acid, in addition to this, by in manufacture The method that the method for mesosome 3-1a is identical has manufactured above-mentioned intermediate 5-1a (40.4g, yield 75%, MS:[M+H]+=239).
(B) manufacture of intermediate 5-1b
Intermediate 1-1a is replaced using intermediate 5-1a, in addition to this, by identical with the method for manufacturing intermediate 1-1b Method manufactured above-mentioned intermediate 5-1b (26.8g, yield 72%, MS:[M+H]+=219).
(C) manufacture of intermediate 5-1c
Intermediate 3-1b is replaced using intermediate 5-1b, in addition to this, by identical with the method for manufacturing intermediate 1-1c Method manufactured above-mentioned intermediate 5-1c (50.1g, yield 81%, MS:[M+H]+=500).
(D) manufacture of intermediate 5-1d
Intermediate 1-1c is replaced using intermediate 5-1c, in addition to this, by identical with the method for manufacturing intermediate 1-1d Method manufactured above-mentioned intermediate 5-1d (30.0g, yield 91%, MS:[M+H]+=329).
2) compound synthesis of intermediate 5-1f
(A) manufacture of intermediate 5-1e
Intermediate 2-1b is replaced using intermediate 5-1d, in addition to this, by identical with the method for manufacturing intermediate 2-2a Method manufactured above-mentioned intermediate 5-1e (17.1g, yield 86%, MS:[M+H]+=434).
(B) manufacture of intermediate 5-1f
Intermediate 1-1e is replaced using intermediate 5-1e, in addition to this, by identical with the method for manufacturing intermediate 1-1f Method manufactured above-mentioned intermediate 5-1f (13.6g, yield 66%, MS:[M+H]+=526).
3) synthesis of compound 17
Intermediate 2-1d is replaced, and use 2- ([1,1'- xenyl] -4- bases) chloro- 6- benzene of -4- using intermediate 5-1f Base -1,3,5-triazines (5a) in addition to this, has been manufactured above-mentioned instead of 2b by the method identical with the method for manufacturing compound 3 Compound 17 (8.2g, yield 89%, MS:[M+H]+=707).
Production Example 18：The manufacture of compound 18
Intermediate 2-1d is replaced, and use 2- chloro- 4- (dibenzo [b, d] furans -3- bases) -6- using intermediate 5-1f Phenyl -1,3,5-triazines (5b) in addition to this, has been manufactured instead of 2b by the method identical with the method for manufacturing compound 3 State compound 18 (7.8g, yield 83%, MS:[M+H]+=721).
Production Example 19：The manufacture of compound 19
1) compound synthesis of intermediate 5-2b
(A) manufacture of intermediate 5-2a
Using intermediate 5-1d and intermediate 2b replace intermediate 1-1d and intermediate 1a, in addition to this, by with manufacture The method that the method for intermediate 1-1e is identical has manufactured above-mentioned intermediate 5-2a (15.2g, yield 77%, MS:[M+H]+= 433)。
(B) manufacture of intermediate 5-2b
Intermediate 1-1e is replaced using intermediate 5-2a, in addition to this, by identical with the method for manufacturing intermediate 1-1f Method manufactured above-mentioned intermediate 5-2b (12.8g, yield 69%, MS:[M+H]+=525).
2) synthesis of compound 19
Intermediate 2-1d is replaced, and use 2- (4- bromophenyls) -4,6- diphenyl -1,3,5- tri- using intermediate 5-2b Piperazine (5c) in addition to this, above compound 19 has been manufactured by the method identical with the method for manufacturing compound 3 instead of 2b (7.0g, yield 81%, MS:[M+H]+=706).
Production Example 20：The manufacture of compound 20
(A) manufacture of intermediate 5-3a
Intermediate 2-1d is replaced, and use 2- chloro- 4- (4- chlorphenyls) -6- phenyl -1,3,5- using intermediate 5-2b Triazine (5d) in addition to this, above-mentioned intermediate 5-3a has been manufactured by the method identical with the method for manufacturing compound 3 instead of 2b (6.5g, yield 80%, MS:[M+H]+=665).
(B) manufacture of compound 20
By intermediate 5-3a (6.5g, 9.79mmol), 1- bromines dibenzo [b, d] furans (5e) (2.7g, 10.8mmol), Pd (t-Bu3P)2(0.1g, 0.20mmol) and the K for being dissolved in water3PO4(5.2g, 24.5mmol) is added to twoIn alkane (150mL), It is refluxed.After 10 hours, after reaction was completed, room temperature is cooled the temperature to, is filtered, removal alkali (base) is washed with water.Utilize N- N-methyl-2-2-pyrrolidone N recrystallizes, so as to obtain above compound 20 (6.1g, yield 78%, MS:[M+H]+=796).
Production Example 21：The manufacture of compound 21
(A) manufacture of intermediate 6-1a
Using dibenzo [b, d] furans -1- ylboronic acids and intermediate 2b replace dibenzo [b, d] furans -3- ylboronic acids and Intermediate 3a in addition to this, above-mentioned intermediate 6-1a has been manufactured by the method identical with the method for manufacturing intermediate 4-1a (107.6g, yield 87%, MS:[M+H]+=400).
(B) manufacture of intermediate 6-1b
Intermediate 4-1a is replaced using intermediate 6-1a, in addition to this, by identical with the method for manufacturing intermediate 4-1b Method manufactured above-mentioned intermediate 6-1b (63.3g, yield 49%, MS:[M+H]+=478).
(C) manufacture of intermediate 6-1c
Intermediate 3-3a is replaced using intermediate 6-1b, in addition to this, by identical with the method for manufacturing intermediate 3-3b Method manufactured above-mentioned intermediate 6-1c (58.0g, yield 83%MS:[M+H]+=526).
(D) manufacture of compound 21
Using intermediate 6-1c and intermediate 2b replace intermediate 1-1f and intermediate 1b, in addition to this, by with manufacture The method that the method for compound 1 is identical has manufactured above compound 21 (15.2g, yield 70%, MS:[M+H]+=631).
Production Example 22：The manufacture of compound 22
Using the 4- chloro- 2- phenylpyridines (6a) of ([1,1'- xenyl] -4- bases) -6- instead of intermediate 2b, in addition to this, Above compound 22 (10.0g, yield 74%, MS have been manufactured by the method identical with the method for manufacturing compound 21:[M+H]+ =706).
Production Example 23：The manufacture of compound 23
Intermediate 2b is replaced using intermediate 3a, in addition to this, passes through the method identical with the method for manufacturing compound 21 Above compound 23 (10.3g, yield 75%, MS are manufactured:[M+H]+=721).
Production Example 24：The manufacture of compound 24
Intermediate 2b is replaced using intermediate 2c, in addition to this, passes through the method identical with the method for manufacturing compound 21 Above compound 24 (9.9g, yield 72%, MS are manufactured:[M+H]+=721).
Production Example 25：The manufacture of compound 25
Intermediate 2b is replaced using intermediate 2d, in addition to this, passes through the method identical with the method for manufacturing compound 21 Above compound 24 (10.7g, yield 80%, MS are manufactured:[M+H]+=707).
Production Example 26：The manufacture of compound 26
Intermediate 2b is replaced using intermediate 1a, in addition to this, passes through the method identical with the method for manufacturing compound 21 Above compound 26 (7.7g, yield 68%, MS are manufactured:[M+H]+=630).
Production Example 27：The manufacture of compound 27
1) manufacture of intermediate 6-1e
(A) manufacture of intermediate 6-1d
(2- cyano-phenyls) boric acid and the chloro- 4- of 2- (4- chlorphenyls) -6- phenyl -1,3,5- triazines is used to replace dibenzo [b, d] furans -3- ylboronic acids and intermediate 3a in addition to this, pass through the method system identical with the method for manufacturing intermediate 4-1a Above-mentioned intermediate 6-1d (10.1g, yield 75%, MS are made:[M+H]+=369).
(B) manufacture of intermediate 6-1e
Intermediate 3-3a is replaced using intermediate 6-1d, in addition to this, by identical with the method for manufacturing intermediate 3-3b Method manufactured above-mentioned intermediate 6-1e (9.5g, yield 75%MS:[M+H]+=461).
2) manufacture of compound 27
Intermediate 6-1c is replaced using intermediate 6-1e, in addition to this, by identical with the method for manufacturing compound 21 Method has manufactured above compound 27 (11.3g, yield 73%, MS:[M+H]+=732).
Production Example 28：The synthesis of compound 28
Intermediate 2b is replaced using intermediate 6-1e, in addition to this, passes through the side identical with the method for manufacturing compound 21 Method has manufactured above compound 28 (7.1g, yield 89%, MS:[M+H]+=732).
Production Example 29：The synthesis of compound 29
(A) manufacture of intermediate 6-2a
Using dibenzo [b, d] furans -1- ylboronic acids and intermediate 5c replace dibenzo [b, d] furans -3- ylboronic acids and Intermediate 3a in addition to this, above-mentioned intermediate 6-2a has been manufactured by the method identical with the method for manufacturing intermediate 4-1a (36.7g, yield 83%, MS:[M+H]+=476).
(B) manufacture of intermediate 6-2b
Intermediate 4-1a is replaced using intermediate 6-2a, in addition to this, by identical with the method for manufacturing intermediate 4-1b Method manufactured above-mentioned intermediate 6-2b (22.0g, yield 52%, MS:[M+H]+=554).
(C) manufacture of intermediate 6-2c
Intermediate 3-3a is replaced using intermediate 6-2b, in addition to this, by identical with the method for manufacturing intermediate 3-3b Method manufactured above-mentioned intermediate 6-2c (17.1g, yield 72%MS:[M+H]+=602).
(D) manufacture of compound 29
Intermediate 6-1c is replaced using intermediate 6-2c, in addition to this, by identical with the method for manufacturing compound 21 Method has manufactured above compound 29 (13.7g, yield 68%, MS:[M+H]+=707).
Production Example 30：The synthesis of compound 30
(A) manufacture of intermediate 6-3a
Using dibenzo [b, d] furans -1- ylboronic acids and intermediate 1a replace dibenzo [b, d] furans -3- ylboronic acids and Intermediate 3a in addition to this, above-mentioned intermediate 6-3a has been manufactured by the method identical with the method for manufacturing intermediate 4-1a (52.8g, yield 80%, MS:[M+H]+=399).
(B) manufacture of intermediate 6-3b
Intermediate 4-1a is replaced using intermediate 6-3a, in addition to this, by identical with the method for manufacturing intermediate 4-1b Method manufactured above-mentioned intermediate 6-3b (31.8g, yield 50%, MS:[M+H]+=477).
(C) manufacture of intermediate 6-3c
Intermediate 3-3a is replaced using intermediate 6-3b, in addition to this, by identical with the method for manufacturing intermediate 3-3b Method manufactured above-mentioned intermediate 6-3c (22.8g, yield 65%MS:[M+H]+=525).
(D) manufacture of compound 30
It is replaced using intermediate 6-3c and 2- ([1,1'- xenyls] -3- bases) -4- chloro-6-phenyl -1,3,5- triazines (6b) Intermediate 6-1c and intermediate 2b in addition to this, above-mentionedization has been manufactured by the method identical with the method for manufacturing compound 21 Close object 30 (9.9g, yield 64%, MS:[M+H]+=706).
Production Example 31：The synthesis of compound 31
Using intermediate 6-3c and intermediate 1c replace intermediate 6-1c and intermediate 2b, in addition to this, by with manufacture The method that the method for compound 21 is identical has manufactured above compound 31 (10.5g, yield 69%, MS:[M+H]+=705).
[experimental example 1]
Embodiment 1
It will be withThickness thin film be coated with the glass substrate of ITO (tin indium oxide, indium tin oxide) and put Enter in the distilled water dissolved with detergent, washed using ultrasonic wave.At this moment, as detergent, Fei Xier companies are used (Fischer Co.) product as distilled water, has used the filter manufactured by Millipore Corp. (Millipore Co.) (Filter) distilled water of filtering twice.After ITO is washed 30 minutes, it is repeated twice with distilled water and carries out 10 minutes ultrasonic waves Washing.After water washing is distilled, after being carried out ultrasonic washing with isopropanol, acetone, methanol solvate and dried, it is delivered to Gas ions cleaning machine.In addition, using oxygen plasma, by aforesaid substrate cleaning after five minutes, vacuum evaporation is delivered the substrate to Machine.
On the ito transparent electrode prepared in this way withThickness thermal vacuum following six nitriles, six azepine benzophenanthrenes are deposited (hexanitrile hexaazatriphenylene；HAT) compound and form hole injection layer.In above-mentioned hole injection layer On withThickness thermal vacuum vapor deposition as the substance of transporting holes 4-4'- bis- [N- (1- naphthalenes)-N- phenylaminos] connection Benzene (NPB；HT-1) form hole transmission layer, and in HT-1 evaporation films withThickness vacuum evaporation HT-2 chemical combination Object and form electronic barrier layer.Then, it is deposited as material of main part and existed altogether using 16% weight ratio in above-mentioned HT-2 evaporation films The compound 1 and the phosphorescent dopants D1 that are manufactured in above-mentioned steps and formedThickness luminescent layer.In above-mentioned luminescent layer On withThickness vacuum evaporation ET-1 substances, further by ET-2 substances and the Li of 2% weight ratio withThickness It is deposited altogether and forms electron transfer layer and electron injecting layer.On above-mentioned electron injecting layer withThickness AM aluminum metallization and Form cathode.
During above-mentioned, the evaporation rate of organic matter maintainsAluminium maintainsVapor deposition Speed, in vapor deposition, vacuum degree maintains 1 × 10-7~5 × 10-8Torr, so as to make organic illuminating element.
Embodiment 2 is to embodiment 21
When forming luminescent layer, as phosphorescent light body material, table 1 below compound represented is used to replace compound 1, In addition to this, the organic illuminating element of embodiment 2 to 21 has been made respectively using the method identical with above-described embodiment 1.It is following In table 1, D2 substances are as follows.
Comparative example 1 to 7
When forming luminescent layer, as material of main part, following C1 as described in Table 2 have been used respectively to C8 replacementizations Object 1 is closed, in addition to this, has made the organic illuminating element of comparative example 1 to 7 respectively by the method identical with above-described embodiment 1.
Electric current is applied to the organic illuminating element made by above-described embodiment 1 to 21 and comparative example 1 to 7, measures this When voltage, efficiency, chromaticity coordinates and service life, and the results are shown in table 1 below and 2.T95 represents that brightness subtracts from original intensity Required time when as low as 95%.
【Table 1】
【Table 2】
As shown in above-mentioned table 1 and 2, can be confirmed by compound according to the present invention be used as luminescent layer material of main part and The situation of the organic illuminating element of manufacture is compared with the organic illuminating element of comparative example, in driving voltage, current efficiency, Yi Jishou Excellent performance is shown in terms of life.
In particular, can be confirmed organic illuminating element involved by embodiment with used as usually used phosphorescence host object Organic illuminating element involved by the comparative example 7 of the compound C8 of matter is compared, and is reduced with the voltage of about 8-16%, in driving electricity Excellent specific property is shown in terms of pressure.Similarly, with 1 and 2 institute of comparative example of two symmetrical compounds of heterocyclic substituent (C1 and C2) The organic illuminating element being related to is compared, and shows low driving voltage.In addition, only there are one replace in two substituent groups are used Base for heterocyclic substituent compound C5 and C6 comparative example 4 and 5 involved by organic illuminating element compared with comparative example 1 and 2, The advantages of showing driving voltage and efficiency, but when compared with the compound of the present invention 6,7,9,11,14,17,22 and 24, this hair Being expressly shown for as little as 105% up to 132% service life increases and shows the advantages of larger in terms of the service life is improved.
In addition, only there are one the compounds of heterocyclic substituent with using for the organic illuminating element involved by embodiment 6 and 11 Organic illuminating element involved by the comparative example 4 of C4 is compared, and is shown minimum more than 30% efficiency and is increased and more than 113% Service life increases.
In addition, embodiment 1,4,7,10,12 and 16 is compared, can be confirmed according to compound in the embodiment mentioned Dibenzofurans the position of substitution, there are voltage and aging variation, and can be confirmed specific position improve the service life.Not only In embodiment 1 to 9, this tendentiousness is also confirmed in the compound of embodiment 10 to 20.Also, by embodiment 15 to 20 into Row compares, according to the L of chemical formula 11-HAr1Or L2-HAr2Substituent group type show that voltage and efficiency characteristic have differences, And it can be seen that in efficiency and voltage, substance excellent in terms of the service life.
As set forth above, it is possible to confirm the compound of the present invention compared with comparative example compound, according to the position of substituent group and With reference to the type of number and substituent group, excellent characteristic is shown in driving voltage and in terms of the service life.
[experimental example 2]
Embodiment 22
It will be withThickness thin film be coated with the glass substrate of ITO (tin indium oxide, indium tin oxide) and put Enter in the distilled water dissolved with detergent, washed using ultrasonic wave.At this moment, as detergent, Fei Xier companies are used (Fischer Co.) product as distilled water, has used the filter manufactured by Millipore Corp. (Millipore Co.) (Filter) distilled water of filtering twice.After IT O are washed 30 minutes, it is repeated twice with distilled water and carries out 10 minutes ultrasounds Wave washs.After water washing is distilled, after being carried out ultrasonic washing with isopropanol, acetone, methanol solvate and dried, it is delivered to Plasma washing machine.In addition, using oxygen plasma, by aforesaid substrate cleaning after five minutes, vacuum evaporation is delivered the substrate to Machine.
On the ito transparent electrode prepared in this way withThickness thermal vacuum vapor deposition following chemical formula six nitriles, six nitrogen Miscellaneous benzophenanthrene (hexaazatriphenylene；HAT hole injection layer) is formed.The vacuum evaporation on above-mentioned hole injection layer Bis- [N- (1- the naphthalenes)-N- phenylaminos] biphenyl (HT-1) of following compound 4-4'- of substance as transporting holesAnd Form hole transmission layer.Then, with film thickness on above-mentioned hole transmission layerBy following BH and BD with 25:1 weight Luminescent layer is formed than carrying out vacuum evaporation.On above-mentioned luminescent layer withThe following compound ET-A of thickness vacuum evaporation And form electron transfer layer.By the compound 1 manufactured in above-mentioned steps and compound L iQ (8- hydroxyls on above-mentioned electron transfer layer Base quinoline lithium, Lithium Quinolate) with 1:1 weight ratio carry out vacuum evaporation and withThickness formed electronics Injection and transport layer.In above-mentioned electron injection and transport layer successively by lithium fluoride (LiF) withThickness, by aluminium withThickness be deposited, so as to form cathode.
In above process, the evaporation rate of organic matter maintainsThe lithium fluoride of cathode maintainsEvaporation rate, aluminium maintainEvaporation rate, vapor deposition when, vacuum degree maintain 2 × 10-7~5 × 10-6Torr, so as to make organic illuminating element.
Embodiment 23 to 35
When forming electron transfer layer, compound 1 is replaced using compound as described in Table 3, in addition to this, is passed through The method identical with above-described embodiment 22 has made the organic illuminating element of embodiment 23 to 35 respectively.
Comparative example 8 to 11
When forming electron transfer layer, compound 1 is replaced using C1, C4, C11 and C12 as shown in table 3 below respectively, is removed Other than this, the organic illuminating element of comparative example 8 to 11 has been made respectively by the method identical with above-described embodiment 22.C1 and C4 Compound it is identical with being used in experimental example 1, the compound of C11 and C12 are as follows.
Electric current is applied to the organic illuminating element made by above-described embodiment 22 to 35 and comparative example 8 to 11, is measured Voltage at this time and efficiency, and the results are shown in Table 3 below.
【Table 3】
By above-mentioned table 3 it is found that can be confirmed using the compound of the present invention as during electron transfer layer substance migration, with using The situation of the compound of comparative example 8 to 11 is compared, and excellent characteristic is shown in terms of high efficiency and stability.
[experimental example 3]
Compound for the Production Example manufactured in above-mentioned steps, determine in the following way HOMO energy levels and PLmax.For the ease of comparing, C8 compounds and C9 compounds are measured also by identical method, C8 compounds and experiment What is used in example 1 is identical, and C9 compounds are as follows.
(1) HOMO energy levels：It is measured by AC-3 equipment.AC-3 has used the Model of Rinken Kei ki companies AC-3, and used on the ito substrate used when making organic illuminating element by material to be determined withThickness Degree carries out the film of vacuum evaporation, the quantum yield for the photon for measuring with the UV intensity illuminations film of 10nW and generating and determine HOMO energy Grade.
(2)PLmaxThe measure of value：It is measured using the sepectrophotofluorometer FP-8600 types of JASCO companies.It is specific and Speech, by material to be determined on bare glass withThickness vacuum evaporation and prepare film, irradiate certain wave on the film Long UV and the wavelength for scanning its releasing.At this moment the highest location determination of intensity is PL in the spectrum obtainedmax.Based on what is obtained PLmaxData, the band gap (Bg) that the obtained initial value of datagram will be excited to be determined as compound.
The above results are shown in table 4 below.In addition, for a part, its result is graphically shown in Fig. 3 extremely In 5.
【Table 4】
HOMO(eV) Bg(eV) PLmax(nm)
Compound 11 6.30 3.25 417
Compound 21 6.21 3.30 405
Compound 22 6.30 3.29 407
Compound 23 6.26 3.28 403
Compound 24 6.06 3.32 406
C8 5.62 2.95 479
C9 5.73 2.97 459
With bipolar (bi-pola r) of luminescent layer (green body material, Green host) that is used in table 4 or N-type spy Property the compound C8 of material of main part compared with C9, have and show and emit in minimum 40nm maximums 76nm shortwaves strong point (emission) feature.In addition, when comparing energy level, it can be confirmed compared with compound C8 and C9, the compound of the present invention tool There are relatively high HOMO energy levels, band gap also goes out greatly about 0.35eV or so.

Claims (19)

1. a kind of compound represented by following chemical formula 1:
Chemical formula 1
In the chemical formula 1,
X is O, S or SiR5R6,
R1aTo R4aIt is each independently L1-HAr1Or A1, R1aTo R4aAt least one of it is above be L1-HAr1,
R1bTo R4bIt is each independently L2-HAr2Or A2, R1bTo R4bAt least one of it is above be L2-HAr2,
R1aFor L1-HAr1When, R1bIt is not L2-HAr2,
R2aFor L1-HAr1When, R2bIt is not L2-HAr2,
R3aFor L1-HAr1When, R3bIt is not L2-HAr2,
R4aFor L1-HAr1When, R4bIt is not L2-HAr2,
L1And L2It is each independently Direct Bonding, substituted or unsubstituted C6-60It arlydene or substituted or unsubstituted includes More than one heteroatomic C in O, N, Si and S2-60Heteroarylidene, but do not include substituted or unsubstituted sub- carbazole Base,
HAr1And HAr2It is each independently any one in following radicals, and comprising N more than at least two,
X1To X3It is each independently N or CR7,
A1、A2、R5To R7、R11And R12It is each independently hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-60Alkane Base, substituted or unsubstituted C1-60Halogenated alkyl, substituted or unsubstituted C1-60Alkoxy, substituted or unsubstituted C1-60It is halogenated Alkoxy, substituted or unsubstituted C3-60Cycloalkyl, substituted or unsubstituted C2-60Alkenyl, substituted or unsubstituted C6-60Aryl, Substituted or unsubstituted C6-60Aryloxy group or more than one substituted or unsubstituted included in N, O and S are heteroatomic C2-60Heterocycle,
N1 is 0 to 3 integer.
2. compound according to claim 1, wherein, X O.
3. compound according to claim 1, wherein,
R1aTo R4aIn one be L1-HAr1, remaining is A1,
R1bTo R4bIn one be L2-HAr2, remaining is A2。
4. compound according to claim 3, wherein,
R1aFor L1-HAr1, R2bFor L2-HAr2；
R1aFor L1-HAr1, R3bFor L2-HAr2；
R1aFor L1-HAr1, R4bFor L2-HAr2；
R2aFor L1-HAr1, R3bFor L2-HAr2；
R2aFor L1-HAr1, R4bFor L2-HAr2；Or
R3aFor L1-HAr1, R4bFor L2-HAr2。
5. compound according to claim 1, wherein, L1And L2It is each independently Direct Bonding or selected from following bases Any one in group：
6. compound according to claim 5, wherein, L1And L2It is each independently Direct Bonding or selected from following bases Any one in group:
7. compound according to claim 1, wherein,
L1For Direct Bonding；
L2For Direct Bonding；Or
L1And L2For Direct Bonding.
8. compound according to claim 1, wherein, HAr1And HAr2It is each independently appointing in following radicals One:
In above-mentioned group,
R7、R11And R12It is each independently hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-20Alkyl, substitution or not Substituted C1-20Halogenated alkyl, substituted or unsubstituted C6-20Aryl or it is substituted or unsubstituted include in N, O and S More than one heteroatomic C2-20Heterocycle.
9. compound according to claim 8, wherein, HAr1And HAr2It is each independently appointing in following radicals One:
In above-mentioned group,
R11And R12It is each independently hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-20Alkyl, substitution do not take The C in generation1-20Halogenated alkyl, substituted or unsubstituted C6-20Aryl or it is substituted or unsubstituted comprising in N, O and S one A above heteroatomic C2-20Heterocycle.
10. compound according to claim 1, wherein, L1-HAr1And L2-HAr2It is each independently selected from following radicals In any one：
11. compound according to claim 1, wherein, A1And A2Be each independently hydrogen, deuterium, halogen, cyano, amino, Substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C1-20Halogenated alkyl or substituted or unsubstituted C6-20Aryl.
12. compound according to claim 11, wherein, A1And A2For hydrogen.
13. compound according to claim 1, wherein, the compound is what is represented by following chemical formula 1-1 to 1-6 Any one in compound:
Chemical formula 1-1
Chemical formula 1-2
Chemical formula 1-3
Chemical formula 1-4
Chemical formula 1-5
Chemical formula 1-6
In the chemical formula 1-1 to 1-6,
For X, L1、L2、HAr1And HAr2Definition it is identical with the definition in claim 1.
14. compound according to claim 1, wherein, the compound is any one in following compounds：
15. a kind of organic illuminating element comprising：First electrode, it is opposed with the first electrode and have second electricity Pole and has 1 layer or more of organic matter layer between the first electrode and the second electrode, in the organic matter layer Any one of 1 layer of claim 1 to 14 contained above described in compound.
16. organic illuminating element according to claim 15 is comprising the organic matter layer of the compound is luminous Layer.
17. organic illuminating element according to claim 16, wherein, the compound as material of main part and comprising.
18. organic illuminating element according to claim 17, wherein, the luminescent layer also includes dopant compound.
19. organic illuminating element according to claim 15 is comprising the organic matter layer of the compound is noted for electronics Enter layer, electron transfer layer or the layer for being carried out at the same time electron injection and electron-transport.
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