CN108922976A - A kind of organic electroluminescence device - Google Patents
A kind of organic electroluminescence device Download PDFInfo
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- CN108922976A CN108922976A CN201810742317.0A CN201810742317A CN108922976A CN 108922976 A CN108922976 A CN 108922976A CN 201810742317 A CN201810742317 A CN 201810742317A CN 108922976 A CN108922976 A CN 108922976A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
Abstract
The present invention provides a kind of organic electroluminescence devices, are related to organic field of photoelectric technology.A kind of organic luminescent device provided by the invention, hole transmission layer include the first compound indicated by formula (1), and electron transfer layer includes the second compound indicated by formula (2).First compound is compound of the arylamine class formation in conjunction with fluorenes class group, has malleable conjugated system and obtains better carrier transmission performance.Second compound is the compound that benzimidazole group connection azepine carbazole group is formed, and continuous pi-conjugated system brings preferable electron mobility, to have high electron mobility.It will be both applied in organic electroluminescence device, and balance the transmission rate in electronics and hole, and improve exciton in the production rate and utilization rate of luminescent layer, reduce the cut-in voltage of device and improve the luminous efficiency of device.
Description
Technical field
The present invention relates to organic photoelectric technical fields, and in particular to a kind of organic electroluminescence device.
Background technique
In recent years, Organic Light Emitting Diode (OLED:Organic Light Emitting Diode) as a kind of novel
The visual field of people is progressed into promising display technology.It is compared with traditional display technology, in voltage characteristic, luminance
Degree, luminous efficiency, device weight, response speed and appreciative perspective etc. have significant advantage, and because of its low cost potential,
Possess broad mass market prospect.
In general, OLED has stratiform or laminar structure.For example, typical OLED has anode/organic luminous layer/cathode more
Layer structure.OLED can also have various other structures, such as anode/hole injection layer/hole transmission layer/luminescent layer/electronics passes
Defeated layer/electron injecting layer/cathode multilayered structure or anode/hole injection layer/hole transmission layer/luminescent layer/hole blocking layer/electricity
Sub- transport layer/electron injecting layer/cathode multilayered structure.
But there is luminous efficiency and service life more in traditional OLED display device, mainly there is following several originals
Cause：On the one hand the matching degree between the luminescent properties and each layer combined material of luminous organic material used is depended on；On the one hand it takes
Certainly in exciton utilization rate, since hole is different with the transmission speed of electronics in organic photoelectrical material, conventional device structure holds very much
Easily there is carrier and inject unbalanced problem, causes electrons and holes combined efficiency low and the offset of recombination region, to lead
The luminous efficiency of cause organic electroluminescence device is low, the service life is low.
As market further increases OLED device requirement, seek higher luminous efficiency, the more long-life, more inexpensive
OLED device become development trend become one so developing a kind of more excellent performance of organic electroluminescence device
Kind urgent problem to be solved.
Summary of the invention
The object of the present invention is to provide the organic electroluminescents of a kind of achievable higher luminous efficiency and low driving voltage
Device.
The present invention provides a kind of organic electroluminescence device, including
Opposed facing anode and cathode,
Luminescent layer between the anode and the cathode,
Hole transmission layer between the anode and the luminescent layer,
Electron transfer layer between the cathode and the luminescent layer,
Wherein, the hole transmission layer includes the first compound indicated by formula (1), and
The electron transfer layer includes the second compound indicated by formula (2)：
In formula, L1The Asia of arlydene, substituted or unsubstituted C3~C30 selected from substituted or unsubstituted C6~C30 is miscellaneous
One of aryl；Ar1、Ar2、Ar3、Ar4It is the independent aryl selected from substituted or unsubstituted C6~C65, substituted or unsubstituted
One of the heteroaryl of C3~C65, and at least one is selected from following group：
Wherein, Ra、RbThe independent alkyl selected from substituted or unsubstituted C1~C10, substituted or unsubstituted C6~C30
Aryl, one of the heteroaryl of substituted or unsubstituted C6~C30；Rc、RdIt is independent to be selected from hydrogen atom, replace or do not take
One of the alkyl of the C1~C10 in generation, aryl of substituted or unsubstituted C6~C30,
X is selected from O, S, NR5Or CR6R7, R5~R7The independent alkyl selected from substituted or unsubstituted C1~C10, replace or
One of the aryl of unsubstituted C6~C30；
In formula, R1、R2The independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C30
Aryl, one of the heteroaryl of substituted or unsubstituted C3~C30；X1~X4It is independent to be selected from carbon atom or nitrogen-atoms；L2
Selected from one of singly-bound, the aryl of substituted or unsubstituted C6~C30.
Preferably, Ar in first compound1、Ar2、Ar3、Ar4At least one is selected from following group：
Preferably, Ar in first compound1、Ar2It is identical, it is selected from following group：
Preferably, Ar in first compound1、Ar3It is identical, it is selected from following group：
Preferably, Ar in first compound1、Ar2、Ar3、Ar4At least one is selected from following group：
Further preferably, L in first compound1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl
It is base, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted
Phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted base, substitution or not
Substituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzo
Furyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted click
One of oxazolyl, substituted or unsubstituted acridinyl, substituted or unsubstituted indyl；
R1、R2It is independent selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or
Unsubstituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, takes substituted or unsubstituted phenanthryl
It is generation or unsubstituted base, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substituted or unsubstituted phonetic
Piperidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substitution or not
Substituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thiophene
Base, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, takes substituted or unsubstituted furyl
Generation or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, substitution
Or unsubstituted acridinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted Yin
One of diindyl base；R3、R4It is independent to be selected from hydrogen atom, methyl, ethyl, isopropyl or tert-butyl；
X is selected from O, S, NR5Or CR6R7, R5~R7It is independent selected from methyl, ethyl, substituted or unsubstituted phenyl, substitution or
Unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted thienyl, substitution
Or it unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substitution or does not take
It is the dibenzothiophene in generation, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, substituted or unsubstituted
Acridinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, in substituted or unsubstituted indyl
It is a kind of.
Preferably, X in the second compound1~X4In at least one be nitrogen-atoms.
Preferably, X in the second compound2、X3In at least one be nitrogen-atoms, X1、X4For carbon atom.
Preferably, its general formula of molecular structure of the second compound is as shown in II or III：
Wherein, R1、R2It is independent selected from methyl, ethyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl, substitution or
Unsubstituted naphthalene, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, takes substituted or unsubstituted anthryl
It is generation or unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted
Phenoxazine thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substitution or
Unsubstituted ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridyl group,
It is substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted
Triazine radical, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, takes substituted or unsubstituted pyrrole radicals
It is generation or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted
Benzofuranyl, substituted or unsubstituted dibenzothiophene, one of substituted or unsubstituted dibenzofuran group.
Further preferably, the L in the second compound2Selected from singly-bound, substituted or unsubstituted phenyl, substituted or unsubstituted
Naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted base in the wrong, substituted or unsubstituted
One of triphenylene.
Beneficial effects of the present invention：
A kind of organic electroluminescence device provided by the invention, hole transmission layer include the first chemical combination indicated by formula (1)
Object and the electron transfer layer include the second compound indicated by formula (2).
First compound of the invention is aromatic amine compounds, and not only division center is arylamine to this compound, also has one
The fluorenes class special groups of series.On the one hand, fluorenes class group is the space structure of 3 D stereo, be can effectively prevent intermolecular
Aggregation, makes compound be not easy to crystallize；It is easily modified in fluorenes class group, the advantage of strong rigidity keeps compound structure more diversified and steady
It is fixed.On the one hand, for classical arylamine class formation in conjunction with fluorenes class group, increased molecular weight obtains high glass transition temperature, has
The conjugated system of ductility obtains better carrier transmission performance.
Second compound of the invention is benzimidazole group connection azepine carbazole group, forms new compound structure.
On the one hand, benzimidazole group is a kind of with good rigid planar structure and pi-electron cloud density abundant and excellent
Electron delocalization environment particular molecule, and the pi-pi accumulation of aromatic ring can make the compound with such group on benzimidazole
With stronger stability；On the one hand, azepine carbazole group has very high triplet energy level (2.96eV) and stable energy level,
The high triplet of carbazole group is not only remained, unsaturated C=N double bond is also introduced into group, improves electron-transport
Ability, by the way that the adjusting to material carrier transmittability even may be implemented from different group keys；On the other hand, benzimidazole
A kind of electron transport material that group is formed in conjunction with azepine carbazole group, increases conjugated system, and biggish molecular weight improves
The glass transition temperature of compound, especially intermediate to be connected using a series of aryl, continuous pi-conjugated system brings preferable electronics
Mobility, so that there is high electron mobility, also, since compound has very big energy gap and high electron mobility,
Not only it can effectively guarantee the injection of electronics, but also can play the role of stopping hole, hole barrier materials and electronics can be made
Transmission material uses.
Organic electroluminescence device of the present invention by the way that the first compound and second compound are combined, thus
The transmission rate of balance electronic and hole improves exciton in the production rate and utilization rate of luminescent layer, avoids carrier and shining
The imbalance of layer avoids device lifetime caused by the heat localization of electron transfer layer and luminous bed boundary from deteriorating, to reduce device
The cut-in voltage of part improves the luminous efficiency and service life of device.
The raw materials of compound that organic electroluminescence device of the present invention uses is easy to get, and synthesis is simple, easy to operate.
Detailed description of the invention
Fig. 1 is a kind of organic electroluminescence device sectional view.
Wherein, 1/ anode of substrate, 2/ hole injection layer, 3/ hole transmission layer, 4/ luminescent layer, 5/ electron transfer layer, 6/ electron injection
7/ cathode 8 of layer.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Alkyl of the present invention refers to alkyl made of minusing a hydrogen atom in alkane molecule, can be straight chain alkane
Base, branched alkyl, naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Aryl of the present invention refers to remove a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule after, be left the total of univalent perssad
Claiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but
It is without being limited thereto.
Heteroaryl of the present invention refers to the group that one or more aromatic core carbon in aryl are substituted by hetero atom
General name, the hetero atom include but is not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl
Base, example may include pyridyl group, pyrrole radicals, pyridyl group, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene
Pheno base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
Substituted alkyl of the present invention, substituted alkoxy, substituted aryl, substituted aryl amine, substituted heteroaryl
In base, the substituent group is independently selected from deuterium, C1-C10 alkyl, cyano, nitro, C6-C24 aryl or C3-C20 heteroaryl.
With reference to Fig. 1, the organic electroluminescence device according to embodiment include anode 2 and cathode 8 facing with each other and
Hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 between anode 2 and cathode 8.
Anode 2 can be made of the conductor with larger work function to be injected with assist holes, and can be such as metal, gold
Belong to oxide and/or conducting polymer.Anode 2 can be metal such as nickel, platinum, vanadium, chromium, copper, zinc and gold or their alloy；Gold
Belong to oxide such as zinc oxide, indium oxide, tin indium oxide, indium zinc oxide etc.；The combination of metal and oxide such as zinc oxide and aluminium；It leads
Electric polymer for example poly- (3 methyl thiophene), poly- (3,4- (bis- oxygroup of ethylidene -1,2-) thiophene), but not limited to this.
Cathode 8 can be made of the conductor with smaller work function to be injected with auxiliary electron, and can be such as metal,
Metal oxide and/or conducting polymer.Cathode 8 can be metal or its alloy, as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium,
Gadolinium, aluminium, silver, tin, lead, caesium, barium etc.；Sandwich such as LiF/Al, LiO2/ Al, LiF/Ca, LiF/Al and BaF2/ Ca, but
It is without being limited thereto.
Hole injection layer 3 between hole transmission layer 4 and anode 2, which can improve the ITO as anode and be used as hole, to be passed
Interfacial characteristics between the organic material of defeated layer 4, and can be by being coated on ITO and the surface covering of uneven ITO
To make the smooth surface of ITO.For example, hole injection layer 3 can choose work function energy level with ITO and hole transmission layer 4
The material of the intermediate value of HOMO energy level, especially with the material of suitable conductivity, to adjust the work function of the ITO as anode
The difference of the HOMO energy level of energy level and hole transmission layer 4.In conjunction with the present invention, the material of hole injection layer 3 can be N4, N4'- biphenyl
Bis- (9- phenyl -9H- carbazole -3- base) xenyl -4, the 4'- diamines of base-N4, N4'-, but not limited to this.
Electron injecting layer 7 is stacked on electron transfer layer 6, so that electronics is injected by cathode, thus improves power efficiency,
And may include commonly used material, without especially limiting, for example, such as LiF, Liq, NaCl, CsF, Li2O, BaO
Material.
Luminescent layer 5 is the organic layer for emitting light, and when using doping system, including main body and dopant.The present invention
In, main body mainly promote electrons and holes in conjunction with and keeping exciton in luminescent layer, and dopant is from by conjunction with obtaining
Exciton effectively emit light.Luminescent layer may include known main body and dopant.When luminescent layer includes main body and dopant
When, the luminescent layer based on 100wt%, the amount of dopant typically about 0.01wt% to about 15wt%, without limiting.Hair
Photosphere can have the thickness of about 20nm to about 70nm.
Known main body can be such as Alq3, CBP (bis- carbazoles of 4,4'-N, N'--biphenyl), PVK (poly- (N- vinyl click
Azoles)), 9,10- bis- (naphthalene -2- base) anthracenes (ADN), TCTA, TPBI (1,3,5- tri- (N- phenylbenzimidazol -2- base) benzene), TBADN
(3- tert-butyl -9,10- bis- (naphthalene -2- base) anthracene), mCP, OXD-7 etc., but it is not limited to this.
Dopant can be at least one of fluorescent dopants and phosphorescent dopants.Phosphorescent dopants can be including
Ir, Pt, Os, Re, Ti, Zr, Hf or the combined metal-organic complex of two or more.The reality of known blue dopant
Example can be F2Irpic、(F2ppy)2Ir(tmd)、Ir(dfppz)3, three difluorenes (fluorenes) (ter-fluorene (fluorene)),
4,4'- bis- (4- diphenylaminostyrene base) biphenyl (DPAVBi), 2,5,8,11- tetra-terts (TBPe), DPVBi etc..
The example of known Red dopants may include PtOEP, Ir (piq)3, BtpIr etc..The example of known green dopant can
To include Ir (ppy)3(ppy=phenylpyridine), Ir (ppy)2(acac)、Ir(mpyp)3Deng.The above is only some examples, unlimited
In this.
Hole transmission layer 4 is the layer for being transferred to hole from anode 2 in luminescent layer 5, and first comprising being indicated by formula (1) changes
Close object：
In formula, L1The Asia of arlydene, substituted or unsubstituted C3~C30 selected from substituted or unsubstituted C6~C30 is miscellaneous
One of aryl；Ar1、Ar2、Ar3、Ar4It is the independent aryl selected from substituted or unsubstituted C6~C65, substituted or unsubstituted
One of the heteroaryl of C3~C65, and at least one is selected from following group：
Wherein, Ra、RbThe independent alkyl selected from substituted or unsubstituted C1~C10, substituted or unsubstituted C6~C30
Aryl, one of the heteroaryl of substituted or unsubstituted C6~C30；Rc、RdIt is independent to be selected from hydrogen atom, replace or do not take
One of the alkyl of the C1~C10 in generation, aryl of substituted or unsubstituted C6~C30,
X is selected from O, S, NR5Or CR6R7, R5~R7The independent alkyl selected from substituted or unsubstituted C1~C10, replace or
One of the aryl of unsubstituted C6~C30.
Electron transfer layer 6 is the layer for being transferred to electronics from cathode 8 in luminescent layer 5, and may include and receive with electronics
The organic compound of functional group's (electron-withdrawing group) can connect nucleophobic metallic compound or their mixture well.
Electron transfer layer includes the second compound indicated by formula (2) in the present invention：
In formula, R1、R2The independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C30
Aryl, one of the heteroaryl of substituted or unsubstituted C3~C30；X1~X4It is independent to be selected from carbon atom or nitrogen-atoms；L2
Selected from one of singly-bound, the aryl of substituted or unsubstituted C6~C30.
Preferably, Ar in first compound1、Ar2、Ar3、Ar4At least one is selected from following group：
Preferably, Ar in first compound1、Ar2It is identical, it is selected from following group：
Preferably, Ar in first compound1、Ar3It is identical, it is selected from following group：
Preferably, Ar in first compound1、Ar2、Ar3、Ar4At least one is selected from following group：
Further preferably, L in first compound1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl
It is base, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted
Phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted base, substitution or not
Substituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzo
Furyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted click
One of oxazolyl, substituted or unsubstituted acridinyl, substituted or unsubstituted indyl；
R1、R2It is independent selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or
Unsubstituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, takes substituted or unsubstituted phenanthryl
It is generation or unsubstituted base, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substituted or unsubstituted phonetic
Piperidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substitution or not
Substituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thiophene
Base, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, takes substituted or unsubstituted furyl
Generation or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, substitution
Or unsubstituted acridinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted Yin
One of diindyl base；R3、R4It is independent to be selected from hydrogen atom, methyl, ethyl, isopropyl or tert-butyl；
X is selected from O, S, NR5Or CR6R7, R5~R7It is independent selected from methyl, ethyl, substituted or unsubstituted phenyl, substitution or
Unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted thienyl, substitution
Or it unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substitution or does not take
It is the dibenzothiophene in generation, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, substituted or unsubstituted
Acridinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, in substituted or unsubstituted indyl
It is a kind of.
Preferably, X in the second compound1~X4In at least one be nitrogen-atoms.
Preferably, X in the second compound2、X3In at least one be nitrogen-atoms, X1、X4For carbon atom.
Preferably, its general formula of molecular structure of the second compound is as shown in II or III：
Wherein, R1、R2It is independent selected from methyl, ethyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl, substitution or
Unsubstituted naphthalene, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, takes substituted or unsubstituted anthryl
It is generation or unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted
Phenoxazine thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substitution or
Unsubstituted ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, substituted or unsubstituted pyridyl group,
It is substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted
Triazine radical, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, takes substituted or unsubstituted pyrrole radicals
It is generation or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted
Benzofuranyl, substituted or unsubstituted dibenzothiophene, one of substituted or unsubstituted dibenzofuran group.
Further preferably, the L in the second compound2Selected from singly-bound, substituted or unsubstituted phenyl, substituted or unsubstituted
Naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted base in the wrong, substituted or unsubstituted
One of triphenylene.
Most preferably, first compound is selected from one of following compounds：
Most preferably, the second compound is selected from one of following compounds：
First compound of formula (1) of the present invention can be collectively referred to as route synthesis by following：
Wherein, L1The Asia of arlydene, substituted or unsubstituted C3~C30 selected from substituted or unsubstituted C6~C30 is miscellaneous
One of aryl；Ar1、Ar2、Ar3、Ar4It is the independent aryl selected from substituted or unsubstituted C6~C65, substituted or unsubstituted
One of the heteroaryl of C3~C65, and at least one is selected from following group：
Wherein, Ra、RbThe independent alkyl selected from substituted or unsubstituted C1~C10, substituted or unsubstituted C6~C30
Aryl, one of the heteroaryl of substituted or unsubstituted C6~C30；Rc、RdIt is independent to be selected from hydrogen atom, replace or do not take
One of the alkyl of the C1~C10 in generation, aryl of substituted or unsubstituted C6~C30,
X is selected from O, S, NR5Or CR6R7, R5~R7The independent alkyl selected from substituted or unsubstituted C1~C10, replace or
One of the aryl of unsubstituted C6~C30.
Above-mentioned synthesis is to be coupled using a bromo-derivative and the compound of amino substitution as starting material via a series of C-C
To target product (1), it is recommended to use Suzuki coupling reaction.Under nitrogen protection, using tetra-triphenylphosphine palladium as catalyst, potassium carbonate
For alkali, tetrahydrofuran is solvent, and reflux is reacted, and obtained intermediate A is anti-with dibromo substituent respectively again with intermediate B
It answers, finally obtains aromatic amine compound.If intermediate A, intermediate B or intermediate C have and sell, use can be directly bought.
The second compound of formula (2) of the present invention can be collectively referred to as route synthesis by following：
In formula, R1、R2The independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C30
Aryl, one of the heteroaryl of substituted or unsubstituted C3~C30；X1~X4It is independent to be selected from carbon atom or nitrogen-atoms；L2
Selected from one of singly-bound, the arlydene of substituted or unsubstituted C6~C30.
According to the present invention, intermediate A is prepared according to method as follows：
The azepine carbazole of bromo is in nitrogen protection, and palladium acetate, tri-tert-butylphosphine are catalyst, and tert-butyl sodium alkoxide is alkali, molten
Agent be toluene under conditions of, reacted with bromo-derivative via C-N coupling reaction, obtain intermediate A；
According to the present invention, intermediate B is prepared according to method as follows：
For 2-Chlorobenzimidazole in nitrogen protection, palladium acetate, tri-tert-butylphosphine are catalyst, and tert-butyl sodium alkoxide is alkali, solvent
Under conditions of toluene, is reacted with bromo-derivative via C-N coupling reaction, obtain intermediate B；
According to the present invention, intermediate C is prepared according to method as follows：
For intermediate B in nitrogen protection, tetra-triphenylphosphine palladium is catalyst, and potassium carbonate is alkali, and tetrahydrofuran is the item of solvent
Under part, intermediate C is obtained by C-C coupling reaction with hypoboric acid compound；
According to the present invention, formula (2) compound is prepared according to method as follows：
For intermediate C in nitrogen protection, tetra-triphenylphosphine palladium is catalyst, and potassium carbonate is alkali, and tetrahydrofuran is the item of solvent
Under part, target product (2) are obtained by C-C coupling reaction with hypoboric acid compound.
Device architecture of the present invention is most preferably as shown in Figure 1：1/ anode of substrate, 2/ hole injection layer, 3/ hole passes
5/ electron transfer layer of defeated 4/ luminescent layer of layer, 6/ electron injecting layer, 7/ cathode 8.Manufacture has the organic electroluminescent of construction same as below
Device：The first compound/AND of formula described in ITO/NPB-DPA/ (1)：A kind of azepine carbazole of DPVBi (2wt%)/described
Second compound/LiF/Al of the formula (2) of class compound/described.
Organic electroluminescence device of the present invention can be widely applied to Display panel, illumination OLED, flexibility OLED, electronics
The fields such as paper, Organophotoreceptor or Organic Thin Film Transistors.
Embodiment 1：The synthesis of compound 1-A6
The synthesis of intermediate a1-6
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to N, N '-diphenylbenzidine (61.5g, 183mmol) and 3-
Solution of bromo- 9, the 9- dimethyl fluorene (49.9g, 183mmol) in degassed toluene (1L), and the mixture is added under reflux
Heat 2 hours.The reaction mixture is cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is dilute
It releases, and is extracted with toluene, and merge organic phase, it is evaporated under vacuum.The residue was carried out via silica gel
Filter, and recrystallize.Obtain intermediate a1-6 (77.3g, yield 80%).
Mass spectrum m/z：528.63 (calculated values：528.68).Theoretical elemental content (%) C39H32N2：C,88.60；H,6.10；
N, 5.30 actual measurements constituent content (%)：C,88.62；H,6.13；N,5.35.The above results confirm that obtaining product is target product.
The synthesis of intermediate b1-6
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to the bromo- 4- benzene of intermediate a1-6 (96.6g, 183mmol) and 1-
Solution of the formonitrile HCN (33.6g, 185mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.It will
The reaction mixture is cooled to room temperature, and is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and uses toluene
It extracts, and merges organic phase, it is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.
Obtain intermediate b1-6 (92.1g, yield 80%).
Mass spectrum m/z：629.73 (calculated values：629.79).Theoretical elemental content (%) C46H35N3：C,87.73；H,5.60；
N, 6.67 actual measurements constituent content (%)：C,87.73；H,5.63；N,6.64.The above results confirm that obtaining product is target product.
The synthesis of intermediate c1-6
The THF of the 1,2- dichloroethanes of 0.8mL, the 1,2- dimethoxy-ethane of 50mL, 500mL are added into reaction flask
Mixed solvent, then thereto be added iodo activation magnesium chips (2.68g, 110mmol) and 1,2- dibromobenzene (25.9g,
110mmol), at 70 DEG C reaction until magnesium react completely, after mixture is cooled to room temperature, be added dropwise to intermediate b1-6
THF (300mL) solution of (62.9g, 100mmol) heats the mixture to 50 DEG C later and reacts 4 hours, then anti-at room temperature
It answers 12 hours.After reaction, 100mL water is added thereto, solvent is removed under reduced pressure after stirring.Then, 500mL is used at 80 DEG C
Heptane stirs residue 2 hours, filters after cooling and obtains solid, successively rinses filter cake using heptane, ethyl alcohol, filter cake is tied again
Crystalline substance obtains intermediate c1-6 (40.8g, yield 53%).
Mass spectrum m/z：787.76 (calculated values：787.78).Theoretical elemental content (%) C52H39BrN2O：C,79.28；H,
4.99；Br,10.14；N,3.56；O, 2.03 actual measurements constituent content (%)：C,79.28；H,4.97；Br,10.14；N,3.56；O,
2.05.The above results confirm that obtaining product is target product.
The synthesis of intermediate d1-6
The THF of the 1,2- dichloroethanes of 0.8mL, the 1,2- dimethoxy-ethane of 50mL, 500mL are added into reaction flask
Then the magnesium chips (2.68g, 110mmol) and 2- bromo biphenyl (12.9g, 110mmol) of iodo activation is added in mixed solvent thereto,
At 70 DEG C reaction until magnesium react completely, after mixture is cooled to room temperature, be added dropwise to intermediate c1-6 (78.7g,
THF (300mL) solution 100mmol) heats the mixture to 50 DEG C later and reacts 4 hours, then reaction 12 is small at room temperature
When.After reaction, 100mL water is added thereto, solvent is removed under reduced pressure after stirring.Then, use 500mL heptane will at 80 DEG C
Residue stirs 2 hours, filters after cooling and obtains solid, successively rinses filter cake using heptane, ethyl alcohol, filter cake is recrystallized to give
Intermediate d1-6 (67.4g, yield 73%).
Mass spectrum m/z：923.96 (calculated values：923.98).Theoretical elemental content (%) C64H47BrN2：C,83.19；H,
5.13；Br,8.65；N, 3.03 actual measurements constituent content (%)：C,83.17；H,5.14；Br,8.65；N,3.04.The above results card
The real product that obtains is target product.
The synthesis of compound 1-A6
By intermediate d1-6 (48.9g, 53mmol), palladium acetate (2.4g, 20mmol), triphenylphosphine (5.6g,
21.3mmol), the N, N- of sodium carbonate (28.14g, 267mmol), benzyltriethylammoinium chloride (7.26g, 32mmol) and 500mL
The mixture of dimethyl acetamide under nitrogen protection, back flow reaction 24 hours.After reaction, it is cooled to room temperature and adds
200mL water continues stirring 30 minutes, filters via diatomite, and filtrate decompression removes solvent, and residue is recrystallized to give target product
Compound 1-A6 (16.6g, 43%)
Mass spectrum m/z：843.09 (calculated values：843.06).Theoretical elemental content (%) C64H46N2：C,91.18；H,5.50；
N, 3.32 actual measurements constituent content (%)：C,91.16；H,5.53；N,3.32.The above results confirm that obtaining product is target product.
Embodiment 2：The synthesis of compound 1-A17
By the N in embodiment 1, N '-diphenylbenzidine changes equimolar N into, N '-biphenyl diamine, 3- bromo- 9,
9- dimethyl fluorene changes the bromo- dibenzofurans of equimolar 2- into, other steps are identical as the synthesis of embodiment 1, obtains target
Product Compound 1-A17.Mass spectrum m/z：816.93 (calculated values：816.98).Theoretical elemental content (%) C61H40N2O：C,
89.68；H,4.93；N,3.43；O, 1.96 actual measurements constituent content (%)：C,89.67；H,4.94；N,3.41；O,1.98.It is above-mentioned
As a result confirm that obtaining product is target product.
Embodiment 3：The synthesis of compound 1-A38
By the N in embodiment 1, N '-diphenylbenzidine changes equimolar compound A into, other steps with embodiment 1
Synthesis it is identical, obtain target product compound 1-A38.Mass spectrum m/z：883.26 (calculated values：883.13).Theoretical elemental content
(%) C67H50N2：C,91.12；H,5.71；N, 3.17 actual measurements constituent content (%)：C,91.13；H,5.72；N,3.15.Above-mentioned knot
Fruit confirms that obtaining product is target product.
Embodiment 4：The synthesis of compound 1-A90
Change the bromo- 4- benzonitrile of 1- in embodiment 1 into the bromo- 3- benzonitrile of equimolar 1-, bromo- 9, the 9- dimethyl fluorene of 3-
Change the bromo- 9- phenyl -9H- carbazole of equimolar 3- into, other steps are identical as the synthesis of embodiment 1, obtain target product
Close object 1-A90.Mass spectrum m/z：892.06 (calculated values：892.09).Theoretical elemental content (%) C67H45N3：C,90.21；H,
5.08；N, 4.71 actual measurements constituent content (%)：C,90.21；H,5.06；N,4.73.The above results confirm that obtaining product is target
Product.
Embodiment 5：The synthesis of compound 1-A97
By the N in embodiment 1, N '-diphenylbenzidine changes the bromo- 9- phenyl -9H- carbazole of equimolar 2,7- bis-, 3- into
Bromo- 9,9- dimethyl fluorene changes the aniline of 3 times of amounts into, and bromo- 4 benzonitrile of 1- changes the bromo- 2- benzonitrile of equimolar 1-, other steps into
It is identical as the synthesis of embodiment 1, obtain target product compound 1-A97.Mass spectrum m/z：816.06 (calculated values：816.00).
Theoretical elemental content (%) C61H41N3：C,89.79；H,5.06；N, 5.15 actual measurements constituent content (%)：C,89.77；H,5.07；
N,5.16.The above results confirm that obtaining product is target product.
Embodiment 6：The synthesis of compound 1-B28
The synthesis of intermediate a2-28
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to Isosorbide-5-Nitrae-two bromo- 2,3,5,6- deuterated benzenes (46.8g,
183mmol) and the solution of aniline (51.0g, 549mmol) in degassed toluene (1L), and the mixture is added under reflux
Heat 2 hours.The reaction mixture is cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is dilute
It releases, and is extracted with toluene, and merge organic phase, it is evaporated under vacuum.The residue was carried out via silica gel
Filter, and recrystallize.Obtain intermediate a2-28 (77.3g, yield 80%).
Mass spectrum m/z：340.43 (calculated values：340.45).Theoretical elemental content (%) C24H16D4N2：C,84.67；H,
7.10；N, 8.23 actual measurements constituent content (%)：C,84.66；H,7.11；N,8.23.The above results confirm that obtaining product is target
Product.
The synthesis of intermediate b2-28
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to intermediate a2-28 (62.2g, 183mmol) and 2- bromine Fluorenone
The solution of (47.9g, 185mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
It answers mixture to be cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is mentioned with toluene
It takes, and merges organic phase, it is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.?
To intermediate b2-28 (71.0g, yield 75%).
Mass spectrum m/z：518.63 (calculated values：518.64).Theoretical elemental content (%) C37H22D4N2O：C,85.68；H,
5.83；N,5.40；O, 3.08 actual measurements constituent content (%)：C,85.67；H,5.83；N,5.42；O,3.08.The above results confirm
Acquisition product is target product.
The synthesis of intermediate c2-28
The THF of the 1,2- dichloroethanes of 0.8mL, the 1,2- dimethoxy-ethane of 50mL, 500mL are added into reaction flask
Mixed solvent, then thereto be added iodo activation magnesium chips (2.68g, 110mmol) and 1,2- dibromobenzene (25.9g,
110mmol), at 70 DEG C reaction until magnesium react completely, after mixture is cooled to room temperature, be added dropwise to intermediate b2-
THF (300mL) solution of 28 (51.8g, 100mmol) heats the mixture to 50 DEG C later and reacts 4 hours, then at room temperature
Reaction 12 hours.After reaction, 100mL water is added thereto, solvent is removed under reduced pressure after stirring.Then, it is used at 80 DEG C
500mL heptane stirs residue 2 hours, filters after cooling and obtains solid, successively rinses filter cake using heptane, ethyl alcohol, will filter
Cake is recrystallized to give intermediate c2-28 (35.7g, yield 53%).
Mass spectrum m/z：675.66 (calculated values：675.65).Theoretical elemental content (%) C43H27BrN2OD4：C,76.44；H,
5.22；Br,11.83；N,4.15；O, 2.37 actual measurements constituent content (%)：C,76.44；H,5.24；Br,11.83；N,4.15；O,
2.35.The above results confirm that obtaining product is target product.
The synthesis of intermediate d2-28
Intermediate c2-28 (51.8g, 100mmol) is put into the reaction flask equipped with 200mL glacial acetic acid, is added with stirring
Benzene (8.58g, 110mmol) continues stirring 24 hours at room temperature.After reaction, 200mL water is added into system, is stirred for
30 minutes, after adjusting pH value to neutrality with saturated sodium bicarbonate solution, methylene chloride extraction merged organic phase, dry concentration, weight
Crystallization obtains intermediate d2-28 (44.1g, yield 60%).
Mass spectrum m/z：735.66 (calculated values：735.74).Theoretical elemental content (%) C49H31BrN2D4：C,79.99；H,
5.34；Br,10.86；N, 3.81 actual measurements constituent content (%)：C,79.97；H,5.34；Br,10.86；N,3.83.The above results
Confirm that obtaining product is target product.
The synthesis of compound 1-B28
By intermediate d2-28 (38.9g, 53mmol), palladium acetate (2.4g, 20mmol), triphenylphosphine (5.6g,
21.3mmol), the N, N- of sodium carbonate (28.14g, 267mmol), benzyltriethylammoinium chloride (7.26g, 32mmol) and 500mL
The mixture of dimethyl acetamide under nitrogen protection, back flow reaction 24 hours.After reaction, it is cooled to room temperature and adds
200mL water continues stirring 30 minutes, filters via diatomite, and filtrate decompression removes solvent, and residue is recrystallized to give target product
Compound 1-B28 (13.8g, 40%)
Mass spectrum m/z：654.89 (calculated values：654.83).Theoretical elemental content (%) C49H30D4N2：C,89.87；H,
5.85；N, 4.28 actual measurements constituent content (%)：C,89.86；H,5.85；N,4.29.The above results confirm that obtaining product is target
Product.
Embodiment 7：The synthesis of compound 2-A1
The synthesis of intermediate A 1-1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) be added to bromo- 5H- pyrido [4, the 3-B] indoles of 7- (45.2g,
183mmol) and the solution of iodobenzene (37.7g, 185mmol) in degassed toluene (1L), and the mixture is added under reflux
Heat 2 hours.The reaction mixture is cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is dilute
It releases, and is extracted with toluene, and merge organic phase, it is evaporated under vacuum.The residue was carried out via silica gel
Filter, and recrystallize.Obtain intermediate A 1-1 (47.2g, yield 80%).
Mass spectrum m/z：323.23 (calculated values：323.19).Theoretical elemental content (%) C17H11N2Br：C,63.18；H,
3.43；Br,24.72；N, 8.67 actual measurements constituent content (%)：C,63.19；H,3.45；Br,24.72；N,8.64.The above results
Confirm that obtaining product is target product.
The synthesis of intermediate B 1-1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to 2-Chlorobenzimidazole (27.8g, 183mmol) and iodobenzene
The solution of (37.7g, 185mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
It answers mixture to be cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is mentioned with toluene
It takes, and merges organic phase, it is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.?
To intermediate B 1-1 (33.5g, yield 80%).
Mass spectrum m/z：228.73 (calculated values：228.68).Theoretical elemental content (%) C13H9N2Cl：C,68.28；H,
3.97；Cl,15.50；N, 12.25 actual measurements constituent content (%)：C,68.27；H,3.97；Cl,15.52；N,12.24.Above-mentioned knot
Fruit confirms that obtaining product is target product.
The synthesis of intermediate C1-1
Intermediate B 1-1 (9.6g, 42.4mmol) is taken to be added in there-necked flask, addition THF 100mL, nitrogen protection, -78
DEG C stirring 30 minutes, then be added n-BuLi (2.5M) 21mL, react 1 hour, add triisopropyl borate ester 7g, low temperature is anti-
It answers 1 hour, is gradually recovered room temperature.Last handling process, 2M hydrochloric acid is added in system makes solution pH value 4-5, standing liquid separation, water layer
It is extracted with ethyl acetate, merges organic layer, be spin-dried for, obtain intermediate C1-1 (8.2g, yield 80%).
Mass spectrum m/z：242.16 (calculated values：242.09).Theoretical elemental content (%) C13H11BN2O2：C,65.59；H,
4.66；B,4.54；N,11.77；O, 13.44 actual measurements constituent content (%)：C,65.58；H,4.66；B,4.55；N,11.77；O,
13.44.The above results confirm that obtaining product is target product.
The synthesis of compound 2-A1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to intermediate A 1-1 (60.4g, 187mmol) and intermediate C1-1
The solution of (44.3g, 183mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
It answers mixture to be cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is mentioned with toluene
It takes, and merges organic phase, it is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.?
To compound 2-A1 (67.8g, yield 85%).
Mass spectrum m/z：436.53 (calculated values：436.51).Theoretical elemental content (%) C30H20N4：C,82.55；H,4.62；
N, 12.84 actual measurements constituent content (%)：C,82.53；H,4.61；N,12.86.The above results confirm to obtain product as target production
Product.
Embodiment 8：The synthesis of compound 2-B2
The synthesis of intermediate A 1-1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) be added to bromo- 5H- pyrido [4, the 3-B] indoles of 7- (45.2g,
183mmol) and the solution of iodobenzene (37.7g, 185mmol) in degassed toluene (1L), and the mixture is added under reflux
Heat 2 hours.The reaction mixture is cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is dilute
It releases, and is extracted with toluene, and merge organic phase, it is evaporated under vacuum.The residue was carried out via silica gel
Filter, and recrystallize.Obtain intermediate A 1-1 (47.2g, yield 80%).
Mass spectrum m/z：323.23 (calculated values：323.19).Theoretical elemental content (%) C17H11N2Br：C,63.18；H,
3.43；Br,24.72；N, 8.67 actual measurements constituent content (%)：C,63.19；H,3.45；Br,24.72；N,8.64.The above results
Confirm that obtaining product is target product.
The synthesis of intermediate B 2-1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to 2-Chlorobenzimidazole (27.8g, 183mmol) and 2- bromonaphthalene
The solution of (38.3g, 185mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
It answers mixture to be cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is mentioned with toluene
It takes, and merges organic phase, it is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.?
To intermediate B 2-1 (40.7g, yield 80%).
Mass spectrum m/z：278.73 (calculated values：278.74).Theoretical elemental content (%) C17H11N2Cl：C,73.25；H,
3.98；Cl,12.72；N, 10.05 actual measurements constituent content (%)：C,73.25；H,3.96；Cl,12.74；N,10.05.Above-mentioned knot
Fruit confirms that obtaining product is target product.
The synthesis of intermediate C2-1
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to two boron of intermediate B 2-1 (50.8g, 183mmol) and Isosorbide-5-Nitrae-benzene
The solution of sour (30.2g, 183mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.It should
Reaction mixture is cooled to room temperature, and is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is mentioned with toluene
It takes, and merges organic phase, it is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.?
To intermediate C2-1 (67.8g, yield 85%).
Mass spectrum m/z：314.13 (calculated values：314.15).Theoretical elemental content (%) C19H15BN2O2：C,72.64；H,
4.81；B,3.44；N,8.92；O, 10.19 actual measurements constituent content (%)：C,72.64；H,4.83；B,3.44；N,8.92；O,
10.17.The above results confirm that obtaining product is target product.
The synthesis of compound 2-B2
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium acetate (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to intermediate A 1-1 (60.4g, 187mmol) and intermediate C2-1
The solution of (57.5g, 183mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
It answers mixture to be cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is mentioned with toluene
It takes, and merges organic phase, it is evaporated under vacuum.The residue is filtered via silica gel, and is recrystallized.?
To compound 2-B2 (82.3g, yield 80%).
Mass spectrum m/z：562.53 (calculated values：562.66).Theoretical elemental content (%) C40H26N4：C,85.38；H,
4.66；N, 9.96 actual measurements constituent content (%)：C,85.37；H,4.67；N,9.96.The above results confirm that obtaining product is target
Product.
Comparative example 1
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and exposure 30 minutes under ultraviolet light,
Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.It is deposited one layer of 60nm's first
The NPB of 20nm is deposited as hole transmission layer, vapor deposition as hole injection layer, evaporation rate 0.1nm/s in NPB-DPA later
Speed is 0.1nm/s, followed by ADN/DPAVBi, doping concentration 2wt%, host material is deposited in the vapor deposition of luminescent layer, mixing
Evaporation rate be 0.1nm/s, dopant material evaporation rate is 0.002nm/s, evaporation thickness 35nm, and 30nm is then deposited
Alq3As electron transfer layer, evaporation rate 0.1nm/s, successively vacuum evaporation LiF and Al is used as yin on the electron transport layer
Pole, with a thickness of 200nm.
Application Example 1：
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and exposure 30 minutes under ultraviolet light,
Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.It is deposited one layer of 60nm's first
The first compound 1-A6 conduct of 20nm is deposited as hole injection layer, evaporation rate 0.1nm/s in NPB-DPA later
Hole transmission layer, evaporation rate 0.1nm/s, followed by the vapor deposition of luminescent layer, mixing vapor deposition ADN/DPAVBi, doping concentration are
2wt%, the evaporation rate of host material are 0.1nm/s, and dopant material evaporation rate is 0.002nm/s, evaporation thickness 35nm,
The second compound 2-A1 of 30nm is deposited later as electron transfer layer, evaporation rate 0.05nm/s, in electron-transport
Successively vacuum evaporation LiF and Al is as cathode on layer, with a thickness of 200nm.
Hole transmission layer and electron transfer layer such as table 1 in Application Example 2-18 enumerates situation and is combined replacement,
He is identical as the production of Application Example 1.
Measurement is according to comparative example 1, the driving voltage of every kind of Organic Light Emitting Diode of Application Example 1-18 and the effect that shines
Rate, specific value are shown in Table 1.
Table 1
| Sample | HT | ET | Driving voltage (V) | Efficiency (cd/A) |
| Comparative example 1 | NPB | Alq3 | 6.6 | 3.2 |
| Application Example 1 | Compound 1-A6 | Compound 2-A1 | 5.7 | 4.7 |
| Application Example 2 | Compound 1-A17 | Compound 2-A1 | 5.2 | 5.4 |
| Application Example 3 | Compound 1-A38 | Compound 2-A1 | 5.2 | 5.6 |
| Application Example 4 | Compound 1-A90 | Compound 2-A1 | 5.3 | 5.7 |
| Application Example 5 | Compound 1-A97 | Compound 2-A1 | 5.5 | 5.0 |
| Application Example 6 | Compound 1-B28 | Compound 2-A1 | 5.4 | 4.9 |
| Application Example 13 | Compound 1-A6 | Compound 2-B1 | 5.6 | 5.0 |
| Application Example 14 | Compound 1-A17 | Compound 2-B1 | 5.2 | 5.7 |
| Application Example 15 | Compound 1-A38 | Compound 2-B1 | 5.1 | 5.8 |
| Application Example 16 | Compound 1-A90 | Compound 2-B1 | 5.3 | 5.7 |
| Application Example 17 | Compound 1-A97 | Compound 2-B1 | 5.5 | 5.3 |
| Application Example 18 | Compound 1-B28 | Compound 2-B1 | 5.3 | 5.1 |
The above result shows that showing height compared with comparative example 1 using the organic electroluminescence device of the compounds of this invention
The advantages of efficiency, low driving voltage is organic electroluminescence device of good performance.
Obviously, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should refer to
It out, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical field
Bright some improvement and modification can also be carried out, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of organic electroluminescence device, including
Opposed facing anode and cathode,
Luminescent layer between the anode and the cathode,
Hole transmission layer between the anode and the luminescent layer,
Electron transfer layer between the cathode and the luminescent layer,
Wherein, the hole transmission layer includes the first compound indicated by formula (1), and
The electron transfer layer includes the second compound indicated by formula (2)：
In formula, L1Arlydene selected from substituted or unsubstituted C6~C30, in the inferior heteroaryl of substituted or unsubstituted C3~C30
One kind；Ar1、Ar2、Ar3、Ar4The independent aryl selected from substituted or unsubstituted C6~C65, substituted or unsubstituted C3~
One of heteroaryl of C65, and at least one is selected from following group：
Wherein, Ra、RbThe virtue of the independent alkyl selected from substituted or unsubstituted C1~C10, substituted or unsubstituted C6~C30
One of base, heteroaryl of substituted or unsubstituted C6~C30；Rc、RdIt is independent selected from hydrogen atom, substituted or unsubstituted
One of the alkyl of C1~C10, aryl of substituted or unsubstituted C6~C30,
X is selected from O, S, NR5Or CR6R7, R5~R7The independent alkyl selected from substituted or unsubstituted C1~C10 replaces or does not take
One of the aryl of C6~C30 in generation；
In formula, R1、R2The virtue of the independent alkyl selected from substituted or unsubstituted C1~C30, substituted or unsubstituted C6~C30
One of base, heteroaryl of substituted or unsubstituted C3~C30；X1~X4It is independent to be selected from carbon atom or nitrogen-atoms；L2It is selected from
One of singly-bound, arlydene of substituted or unsubstituted C6~C30.
2. a kind of organic electroluminescence device according to claim 1, which is characterized in that Ar in first compound1、
Ar2、Ar3、Ar4At least one is selected from following group：
3. a kind of organic electroluminescence device according to claim 1, which is characterized in that Ar in first compound1、
Ar2It is identical, it is selected from following group：
4. a kind of organic electroluminescence device according to claim 1, which is characterized in that Ar in first compound1、
Ar3It is identical, it is selected from following group：
5. a kind of organic electroluminescence device according to claim 1, which is characterized in that Ar in first compound1、
Ar2、Ar3、Ar4At least one is selected from following group：
6. a kind of organic electroluminescence device according to claim 1, which is characterized in that L in first compound1Choosing
From substituted or unsubstituted phenyl, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted
Naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substitution or not
Substituted pyrenyl, substituted or unsubstituted base, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substitution
Or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzothiophene, substitution
Or it is unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, substituted or unsubstituted acridinyl, substituted or unsubstituted
One of indyl；
R1、R2It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substitution or do not take
The anthryl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substitution or
Unsubstituted base, substituted or unsubstituted ferrosin base, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine
Base, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine radical, substitution do not take
The pyrrole radicals in generation, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substituted or unsubstituted thiophene
Base, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, takes substituted or unsubstituted furyl
Generation or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, substitution
Or unsubstituted acridinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted Yin
One of diindyl base；R3、R4It is independent to be selected from hydrogen atom, methyl, ethyl, isopropyl or tert-butyl；
X is selected from O, S, NR5Or CR6R7, R5~R7It is independent to be selected from methyl, ethyl, substituted or unsubstituted phenyl, substitution or do not take
The naphthalene in generation, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted thienyl, substitution or not
It is substituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted
Dibenzothiophene, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted carbazyl, substituted or unsubstituted a word used for translation
Piperidinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, one in substituted or unsubstituted indyl
Kind.
7. a kind of organic electroluminescence device according to claim 1, which is characterized in that X in the second compound1~
X4In at least one be nitrogen-atoms.
8. a kind of organic electroluminescence device according to claim 1, which is characterized in that X in the second compound2、X3
In at least one be nitrogen-atoms, X1、X4For carbon atom.
9. a kind of organic electroluminescence device according to claim 1, which is characterized in that its molecule of the second compound
General structure is as shown in II or III：
Wherein, R1、R2It is independent to be selected from methyl, ethyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl, substitution or do not take
The naphthalene in generation, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substitution or
Unsubstituted acridinyl, substituted or unsubstituted phenoxazine base, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted pheno
It dislikes thiophene base, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazyl, substituted or unsubstituted pyrenyl, substitution or does not take
Ferrosin base, substituted or unsubstituted base, substituted or unsubstituted acenaphthenyl, the substituted or unsubstituted pyridyl group, substitution in generation
Or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazine
Base, substituted or unsubstituted pyrrole radicals, substituted or unsubstituted benzopyrrole base, substituted or unsubstituted triazolyl, substitution or
Unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzene
And one of furyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran group.
10. a kind of organic electroluminescence device according to claim 1, which is characterized in that the L in the second compound2
It does not take selected from singly-bound, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substitution or
One of the phenanthryl in generation, substituted or unsubstituted base in the wrong, substituted or unsubstituted triphenylene.
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| CN201810742317.0A CN108922976A (en) | 2018-07-09 | 2018-07-09 | A kind of organic electroluminescence device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503636A (en) * | 2018-06-06 | 2018-09-07 | 长春海谱润斯科技有限公司 | A kind of electron transport material and its organic luminescent device |
| CN114122299A (en) * | 2020-06-29 | 2022-03-01 | 江苏三月科技股份有限公司 | Organic electroluminescent device |
-
2018
- 2018-07-09 CN CN201810742317.0A patent/CN108922976A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503636A (en) * | 2018-06-06 | 2018-09-07 | 长春海谱润斯科技有限公司 | A kind of electron transport material and its organic luminescent device |
| CN114122299A (en) * | 2020-06-29 | 2022-03-01 | 江苏三月科技股份有限公司 | Organic electroluminescent device |
| CN114122299B (en) * | 2020-06-29 | 2023-12-29 | 江苏三月科技股份有限公司 | Organic electroluminescent device |
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Application publication date: 20181130 |