CN108329286A - A kind of dopant material and its organic electroluminescence device - Google Patents

A kind of dopant material and its organic electroluminescence device Download PDF

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CN108329286A
CN108329286A CN201810148775.1A CN201810148775A CN108329286A CN 108329286 A CN108329286 A CN 108329286A CN 201810148775 A CN201810148775 A CN 201810148775A CN 108329286 A CN108329286 A CN 108329286A
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unsubstituted
substituted
aryl
heteroaryl
cyano
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蔡辉
孙敬
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Changchun Haipurunsi Technology Co Ltd
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Changchun Haipurunsi Technology Co Ltd
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Abstract

The invention discloses a kind of dopant material and its organic electroluminescence devices, are related to organic optoelectronic materials technology.It is an advantage of the invention that, the dopant material that the host material group with good electron donor property is built up shown in dopant and formula II shown in the structural formula I of the present invention with good electron acceptor property is under lower doping concentration with higher hole mobility, higher conductivity, and with preferable whole thermal stability and dissolubility, be conducive to material filming.The organic electroluminescence device of the present invention includes cathode, anode and one or more organic matter layers, organic matter layer is between cathode and anode, at least one layer in organic matter layer contains the dopant material of the present invention, the organic electroluminescence device of the present invention has lower driving voltage, higher luminous efficiency and luminous brightness, and there is longer service life.

Description

A kind of dopant material and its organic electroluminescence device
Technical field
The present invention relates to organic photoelectrical material technical fields, and in particular to a kind of dopant material and its organic electroluminescence Part.
Background technology
Organic photoelectrical material is the organic material of the generation with photon and electronics, conversion and transmission characteristic.Currently, organic Photoelectric material has been applied to organic electroluminescence device (Organic Light-Emitting Diode, OLED).OLED is Refer to the device that organic photoelectrical material shines under the action of electric current or electric field, electric energy can be converted into luminous energy by it.In recent years Carry out OLED just to receive more and more attention as FPD of new generation and solid state lighting technology.Compared to liquid crystal display skill Art, OLED are shone with its low-power consumption, actively, fast response time, high contrast, no angle limit, can make the spies such as Flexible Displays Point is increasingly used in display and lighting area.
Usual OLED has a multilayered structure, including tin indium oxide (ITO) anode and metallic cathode and be placed in ito anode with Several organic photovoltaic layers between metallic cathode, such as hole injection layer (HIL), hole transmission layer (HTL), luminescent layer (EML), electron transfer layer (ETL) and electron injecting layer (EIL) etc..Under certain voltage driving, electronics is with hole respectively by the moon Pole is injected into electron transfer layer and hole transmission layer with anode, and the two passes through electron transfer layer respectively and hole transmission layer moves to Luminescent layer forms the compound exciton of electron-hole, the form that exciton passes through luminescence relaxation when the two meets combination in luminescent layer Ground state is returned to, it is luminous to achieve the purpose that.
As the hole transmission layer in OLED, basic role is the efficiency of transmission of raising hole in the devices, and will be electric Son is effectively blocked in luminescent layer, realizes that the maximum of carrier is compound；Reduce energy wall of the hole in injection process simultaneously It builds, the injection efficiency in hole is improved, to improve brightness, efficiency and the service life of device.
Currently, usually there is the problems such as operation voltage is high, luminous efficiency is low, service life is short in organic electroluminescence device. Thus, it is that those skilled in the art study all the time to explore the new organic photoelectrical material for organic electroluminescence device Emphasis direction.
For hole transmission layer, traditionally most of material used is undoped hole mobile material, hole Mobility is relatively low, and Chang Wufa provides the satisfactory characteristics of luminescence, therefore, it is still necessary to design the better hole transport of new performance Material is to improve the performance of organic electroluminescence device.
Invention content
Goal of the invention：In view of the above-mentioned problems, the object of the present invention is to provide a kind of dopant materials, dopant is added to base The dopant material that group is built up in material has higher hole mobility, shows the good characteristics of luminescence；The present invention's is another There is provided a kind of organic electroluminescence devices for one purpose, and the organic matter layer of the organic electroluminescence device includes above-mentioned hair Bright dopant material, the organic electroluminescence device have preferable performance.
The above-mentioned technical purpose of the present invention is achieved through the following technical solutions：A kind of dopant material, including dopant And host material, wherein dopant has general structure shown in structural formula I：
Wherein, R1、R2Independent fat-based selected from substituted or unsubstituted C1~C15, substituted or unsubstituted C6~ The aryl of C60, substituted or unsubstituted C3~C60 heteroaryl in one kind；R3、R4、R5、R6It is independent to be selected from cyano, halogen Element, trifluoromethyl, trifluoromethoxy, nitro, the fat-based of substituted or unsubstituted C1~C60, substituted or unsubstituted C6~ The aryl of C60, substituted or unsubstituted C3~C60 heteroaryl in one kind；Ar7、Ar8It is independent selected from substitution or unsubstituted The fat-based of C1-C12, the aryl of substituted or unsubstituted C6~C60, substituted or unsubstituted C3~C60 heteroaryl in It is a kind of；
Wherein host material has general structure shown in formula II：
X is selected from C (R)2、NR、P(O)R、PR、S、SO、SO2、Si(R)2, one kind in O, wherein R is selected from substitution or unsubstituted The alkyl of C1~C15, the aryl of substituted or unsubstituted C6~C24, substituted or unsubstituted C3~C24 heteroaryl in It is a kind of；A is hydrogen, condenses the aryl of substituted or unsubstituted C6~C60 on phenyl ring, condenses the substitution on phenyl ring or do not take One kind in the heteroaryl of the C3~C60 in generation；Ar1、Ar2、Ar3Independent aryl selected from substituted or unsubstituted C6~C60, One kind in the heteroaryl of substituted or unsubstituted C3~C60.
Preferably, the Ar in structural formula I7、Ar8Independently selected from substituted or unsubstituted C6-C12 aryl, substitution or not One kind in the heteroaryl of substituted C3-C12；
X in formula II is selected from C (R)2、NR、S、Si(R)2, one kind in O, wherein R is selected from substituted or unsubstituted C1 The alkyl of~C10, the aryl of substituted or unsubstituted C6~C18, substituted or unsubstituted C3~C18 heteroaryl in one Kind；The A is hydrogen, condenses aryl, the substituted or unsubstituted C3~C30 of substituted or unsubstituted C6~C30 on phenyl ring Heteroaryl in one kind；Ar1、Ar2、Ar3Independent aryl selected from substituted or unsubstituted C6~C30, substitution or unsubstituted C3~C30 heteroaryl in one kind.
Preferably, the Ar in structural formula I7、Ar8Selected from phenyl；
X in formula II is selected from C (R)2, one kind in NR, S, O, wherein R is selected from substituted or unsubstituted C1~C8's Alkyl, the aryl of substituted or unsubstituted C6~C12, substituted or unsubstituted C3~C12 heteroaryl in one kind；A be hydrogen, Condense the aryl of substituted or unsubstituted C6~C18 on phenyl ring, the substituted or unsubstituted C6~C18 condensed on phenyl ring Heteroaryl in one kind；The Ar1、Ar2、Ar3Independent aryl selected from substituted or unsubstituted C6~C18, substitution or not One kind in the heteroaryl of substituted C3~C18.
Preferably, the R in structural formula I3、R4、R5、R6Hydrogen on cyano, C is all by halogen, cyano, three The C3- that methyl fluoride, the aryl of C6-C30 of trifluoromethoxy substitution or the hydrogen on C are all replaced by halogen, cyano, trifluoromethyl The heteroaryl of C30；
X in formula II is selected from C (R)2、NR、S、Si(R)2, one kind in O, wherein R it is independent selected from methyl, ethyl, Propyl, isopropyl, butyl, tertiary butyl, benzyl, phenethyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridine Base, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazine radical, substitution do not take The furyl in generation, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrole radicals.
Preferably, the R in structural formula I3、R4、R5、R6Independently selected from cyano or following group：
Wherein, Z1、Z2、Z3、Z4、Z5、Z6、Z7Independently selected from halogen, cyano, trifluoromethyl, trifluoromethoxy；
A in formula II is selected from hydrogen, substituted or unsubstituted phenyl；
Preferably, the R in structural formula I3With R4It is asynchronously cyano, but at least one is cyano；R5With R6It is asynchronously Cyano, but at least one is cyano；
Ar in formula II1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl Base, substituted or unsubstituted naphthalene, substituted or unsubstituted terphenyl, substituted or unsubstituted carbazyl, substitution do not take The anthryl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substitution or Two fluorenyl of unsubstituted spiral shell, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furans Base, substituted or unsubstituted thienyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofurans Base, substituted or unsubstituted quinolyl.
Preferably, the R in the structural formula I1、R2Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary Butyl, tertiary butyl, isobutyl group or following group：
Wherein, X1、X2、X3、X4、X5、X6、X7、X8、X9Independently selected from hydrogen, halogen, cyano, trifluoromethyl, trifluoro methoxy The alkoxy of base, the alkyl of C1-C4, C1-C4；Y is selected from fat-based, the aryl of C6-C12 or the heteroaryl of C3-C12 of C1-C4.
Most preferably, the one kind of the dopant of structural formula I in chemical constitution as follows：
Most preferably, the one kind of the host material of formula II in chemical constitution as follows：
Further, the present invention also provides a kind of organic electroluminescence device, organic electroluminescence device include cathode, Anode and one or more organic matter layers, between cathode and anode, at least one layer in organic matter layer contains organic matter layer There is the dopant material of aforementioned present invention.
Preferably, organic matter layer includes hole transmission layer, and hole transmission layer includes the dopant material of aforementioned present invention.
Advantageous effect：Compared with prior art, it is an advantage of the invention that having shown in the structural formula I of the present invention good Shown in the dopant and formula II of electron acceptor property with good electron donor property host material purity compared with The energy level of height, the two is appropriate, with good stability in air, and with preferable processability etc..Dopant Dopant material is built up with host material group, dopant generates hole by the electronic transfer process in host material, leads to base The conductivity of material increases with the raising of the quantity and mobility in hole.In addition dopant material of the invention is lower There is higher hole mobility, higher conductivity, and with preferable whole thermal stability and dissolving under doping concentration Property, be conducive to material filming.Organic electroluminescence device using the dopant material of the present invention as organic matter layer has relatively low Driving voltage, higher luminous efficiency and luminous brightness, and have longer service life.
Specific implementation mode
With reference to specific embodiment, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate the present invention Rather than limit the scope of the invention, after having read the present invention, various equivalences of the those skilled in the art to the present invention The modification of form falls within the application range as defined in the appended claims.
A kind of dopant material, including dopant and host material, wherein dopant have structure shown in structural formula I logical Formula：
Wherein, the R1、R2Independent fat-based selected from substituted or unsubstituted C1~C15, substituted or unsubstituted C6 The aryl of~C60, substituted or unsubstituted C3~C60 heteroaryl in one kind；The R3、R4、R5、R6It is independent to be selected from cyanogen The fat-based, substituted or unsubstituted of base, halogen, trifluoromethyl, trifluoromethoxy, nitro, substituted or unsubstituted C1~C60 The aryl of C6~C60, substituted or unsubstituted C3~C60 heteroaryl in one kind；The Ar7、Ar8It is independent to be selected from substitution Or the fat-based of unsubstituted C1-C12, the aryl of substituted or unsubstituted C6~C60, substituted or unsubstituted C3~C60's is miscellaneous One kind in aryl；
Wherein host material has general structure shown in formula II：
X is selected from C (R)2、NR、P(O)R、PR、S、SO、SO2、Si(R)2, one kind in O, wherein R is selected from substitution or unsubstituted The alkyl of C1~C15, the aryl of substituted or unsubstituted C6~C24, substituted or unsubstituted C3~C24 heteroaryl in It is a kind of；
A is hydrogen, condense the aryl of substituted or unsubstituted C6~C60 on phenyl ring, condense substitution on phenyl ring or One kind in the heteroaryl of unsubstituted C3~C60；The Ar1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted C6~C60 Aryl, substituted or unsubstituted C3~C60 heteroaryl in one kind.
Preferably, the Ar in structural formula I7、Ar8Independently selected from substituted or unsubstituted C6-C12 aryl, substitution or not The heteroaryl of substituted C3-C12；
X in formula II is selected from C (R)2、NR、S、Si(R)2, one kind in O, wherein R is selected from substituted or unsubstituted C1 The alkyl of~C10, the aryl of substituted or unsubstituted C6~C18, substituted or unsubstituted C3~C18 heteroaryl in one Kind；A is hydrogen, the aryl for condensing substituted or unsubstituted C6~C30 on phenyl ring, the substitution or unsubstituted condensed on phenyl ring C3~C30 heteroaryl in one kind；Ar1、Ar2、Ar3Independent aryl selected from substituted or unsubstituted C6~C30 takes One kind in the heteroaryl of generation or unsubstituted C3~C30.
Preferably, the Ar in structural formula I7、Ar8Selected from phenyl
X in formula II is selected from C (R)2, one kind in NR, S, O, wherein R is selected from substituted or unsubstituted C1~C8's Alkyl, the aryl of substituted or unsubstituted C6~C12, substituted or unsubstituted C3~C12 heteroaryl in one kind；A be hydrogen, Condense the aryl of substituted or unsubstituted C6~C18 on phenyl ring, the substituted or unsubstituted C6~C18 condensed on phenyl ring Heteroaryl in one kind；Ar1、Ar2、Ar3Independent aryl selected from substituted or unsubstituted C6~C18, substitution or unsubstituted C3~C18 heteroaryl in one kind.
Preferably, the R in structural formula I3、R4、R5、R6Hydrogen on cyano, C is all by halogen, cyano, three The C3- that methyl fluoride, the aryl of C6-C30 of trifluoromethoxy substitution or the hydrogen on C are all replaced by halogen, cyano, trifluoromethyl The heteroaryl of C30；
X in formula II is selected from C (R)2、NR、S、Si(R)2, one kind in O, wherein R it is independent selected from methyl, ethyl, Propyl, isopropyl, butyl, tertiary butyl, benzyl, phenethyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridine Base, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazine radical, substitution do not take The furyl in generation, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrole radicals.
Preferably, the R in structural formula I3、R4、R5、R6Independently selected from cyano or following group：
Wherein, Z1、Z2、Z3、Z4、Z5、Z6、Z7Independently selected from halogen, cyano, trifluoromethyl, trifluoromethoxy；
A in formula II is selected from hydrogen, substituted or unsubstituted phenyl；
Preferably, the R in structural formula I3With R4It is asynchronously cyano, but at least one is cyano；R5With R6It is asynchronously Cyano, but at least one is cyano；
Ar in formula II1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl Base, substituted or unsubstituted naphthalene, substituted or unsubstituted terphenyl, substituted or unsubstituted carbazyl, substitution do not take The anthryl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substitution or Two fluorenyl of unsubstituted spiral shell, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furans Base, substituted or unsubstituted thienyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofurans Base, substituted or unsubstituted quinolyl.
Preferably, the R in structural formula I1、R2Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, tertiary butyl, isobutyl group or following group：
Wherein, X1、X2、X3、X4、X5、X6、X7、X8、X9Independently selected from hydrogen, halogen, cyano, trifluoromethyl, trifluoro methoxy The alkoxy of base, the alkyl of C1-C4, C1-C4；Y is selected from fat-based, the aryl of C6-C12 or the heteroaryl of C3-C12 of C1-C4.
According to the present invention, the substituent group on A rings be selected from hydrogen, deuterium, the alkoxy of C1~C10, the alkyl of C1~C10, C3~ The naphthenic base of C20, the aryl of C6~C24, the aryloxy group of C6~C24, the arylthio of C6~C24, the heteroaryl of C3~C24, C3 One kind in the heterocycle of~C20；
Substituent group on R selects the naphthenic base of hydrogen, deuterium, the alkoxy of C1~C10, the alkyl of C1~C10, C3~C20.
Ar1、Ar2、Ar3On substituent group be selected from hydrogen, deuterium, the alkoxy of C1~C10, the alkyl of C1~C10, C3~C20 The aryl of naphthenic base, C6~C12.
Fat-based of the present invention refers to the fat-based lacked one or several hydrogen atoms from fatty hydrocarbon molecule and formed, Fat-based can also be further divided into alkyl, alkenyl, alkynyl etc..
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, aralkyl, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding Base, tertiary butyl, amyl, isopentyl, cyclopenta, cyclohexyl, benzyl, phenethyl etc., but not limited to this.
Aryl of the present invention refer to aromatic hydrocarbon molecule aromatic core carbon on minus a hydrogen atom after, be left univalent perssad it is total 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 of aryl aromatic core carbon is substituted by hetero atom General name, the hetero atom include but not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl Base, example may include 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.
As an example, it is not particularly limited, the dopant of structural formula I is in chemical constitution as follows in the present invention It is a kind of：
As an example, it is not particularly limited, the one kind of the host material of formula II in chemical constitution as follows：
The synthetic route of the dopant of the structural formula I of the present invention is as follows：
Compound F1, I-R is added into flask1、I-R2, cesium carbonate and DMF, normal-temperature reaction 24 hours, after reaction, Filtering, concentration carry out column chromatography with the mixed liquor of ethyl acetate and dichloromethane, and crude product dichloromethane and methanol carry out weight Crystallization, obtains intermediate S.
In ice-water bath, intermediate S, C (R are added into flask3R4)、C(R5R6), titanium tetrachloride, pyridine and dichloromethane Alkane, low temperature stir 24 hours, add water to flask after reaction, are used in combination dichloromethane to extract organic phase and are used after organic phase concentration The mixed solution of ethyl acetate and hexane carries out column chromatography, and crude product is recrystallized with dichloromethane and petroleum ether, filtered To structural formula I compounds represented.
The synthetic route of the host material of the formula II of the present invention is as follows：
Under protection of argon gas, compound E-1, compound E-2, sodium tert-butoxide, three (dibenzylidenes third are added into flask Ketone) two palladiums, the bis- diphenyl phosphines of 1,1'- dinaphthalenes -2,2'- and toluene, react 24 hours under conditions of 130 DEG C.After cooling, it will mix Object is filtered, and filtrate is concentrated under reduced pressure.The crude product of gained is subjected to column purification, is recrystallized with toluene, by it It after filtering, is dried, as a result obtains intermediate Sub1.
Under protection of argon gas, compound E-3, compound E, sodium tert-butoxide, bis- (triphenylphosphine) dichloros are added into flask Change palladium (II) and dimethylbenzene, is reacted 24 hours under conditions of 130 DEG C.After cooling, water is added, mixture is filtered, it will Filtrate is extracted with toluene, and organic phase is dried with anhydrous magnesium sulfate.It is concentrated under reduced pressure, it is pure that the crude product of gained is carried out column Change, is recrystallized with toluene, after being filtered, be dried, as a result obtain intermediate Sub2.
Under protection of argon gas, intermediate Sub1, intermediate Sub2, sodium tert-butoxide, three (dibenzylidenes third are added into flask Ketone) two palladiums, tri-tert-butylphosphine and dehydrated toluene, react 2 hours at 80 DEG C.After cooling, water is added, mixture was carried out Filter, filtrate is extracted with toluene, organic phase is dried with anhydrous magnesium sulfate.Be concentrated under reduced pressure, by the crude product of gained into Row column purification, is recrystallized with toluene, after being filtered, is dried, and the product of formula II is as a result obtained.
The synthetic route of the host material of dopant and formula II to the structural formula I of the present invention is not particularly limited, Popular response well-known to those skilled in the art may be used.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device include cathode, anode with And one or more organic matter layers, between cathode and anode, at least one layer in organic matter layer contains above-mentioned organic matter layer The dopant material of the present invention.
The organic matter layer of the organic electroluminescence device of the present invention has single layer structure, or optionally has wherein two The multilayered structure of a or more organic matter layer layering.The organic electroluminescence device of the present invention can have hole injection layer, sky Cave transport layer, luminous material layer, electron transfer layer, electron injecting layer or the buffer layer work being placed between anode and hole injection layer For organic matter layer.However, the structure of organic electroluminescence device is without being limited thereto, but it may include small number of organic matter layer. The thickness of the organic matter layer of dopant material containing the present invention is more preferably not higher than 6 μm, preferably not higher than 0.3 μm 0.002~0.3 μm.If desired, the organic matter layer of the dopant material containing the present invention can further include as is generally known in the art Can carry out hole injection, hole transport, shine, the other materials of electron-transport and electron injection.
The organic electroluminescence device of the present invention can be prepared by known methods using known materials, only can be at one layer Or include the dopant material of the present invention in multilayer organic matter layer.
The dopant material of the present invention specifically can be as the hole transmission layer for preparing organic electroluminescence device.What is used has Organic electroluminescence devices are preferably：The ITO on transparent glass is attached to as anode, dopant material of the invention is passed as hole Defeated layer, luminous material layer, hole blocking layer, electron transfer layer, metallic cathode.
The organic electroluminescence device of the present invention can be widely applied to FPD, solid state lighting, Organophotoreceptor or have The fields such as machine thin film transistor (TFT).
The present invention is not particularly limited the raw material employed in following embodiment, can be for commercial product or using this Preparation method known to field technology personnel is prepared.
Synthetic example 1：
The preparation of compound I-1
Compound F (14.41g, 50mmol), compound F1-1 (28.39g, 200mmol), cesium carbonate are added into flask (48.87g, 150mmol) and DMF (433ml), normal-temperature reaction 24 hours filter after reaction, concentration, with ethyl acetate and The mixed liquor of dichloromethane carries out column chromatography, and crude product is recrystallized with dichloromethane and methanol, obtains intermediate S1 (14.24g, 90%).
In ice-water bath, intermediate S1 (5.48g, 17.34mmol), compound F1-2 are added into 250ml flasks (16.37g, 79.03mmol), titanium tetrachloride (29.98g, 158.05mmol), pyridine (12.5g, 158.05mmol) and dichloromethane Alkane (100ml), low temperature stir 24 hours, add water to flask after reaction, and dichloromethane is used in combination to extract organic phase, and organic phase is dense After contracting, column chromatography is carried out with the mixed solution of ethyl acetate and hexane, crude product is recrystallized with dichloromethane and petroleum ether, Compound I-1 (3.73g, 31%) is obtained by filtration.Mass spectrum m/z：Theoretical value：694.52；Measured value：696.63.Theoretical elemental contains Measure (%) C36H16F10N4：C,62.26；H,2.32；F,27.35；N,8.07；Survey constituent content (%)：C,62.24；H, 2.37；F,27.33；N,8.06.The above results confirm that it is target product to obtain product.
Synthetic example 2：
The preparation of compound I-18
It is other to be carried out similarly instead in addition in synthetic example 1, being replaced other than compound F1-1 using compound F2-1 It answers, as a result obtains compound I-18 (4.52g, 30%).Mass spectrum m/z：Theoretical value：868.70；Measured value：867.53.Theoretical member Cellulose content (%) C48H18F10N6：C,66.37；H,2.09；F,21.87；N,9.67；Survey constituent content (%)：C,66.35；H, 2.15；F,21.85；N,9.65.The above results confirm that it is target product to obtain product.
Synthetic example 3：
The preparation of compound I-22
In addition in synthetic example 1, replacing compound F1-1, compound F3-2 to replace compound using compound F3-1 It is other to be carried out similarly reaction other than F1-2, as a result obtain compound I-22 (4.3g, 28%).Mass spectrum m/z：Theoretical value： 886.46；Measured value：888.42.Theoretical elemental content (%) C44H18Cl4F6N6：C,59.62；H,2.05；Cl,16.00；F, 12.86；N,9.48；Survey constituent content (%)：C,59.60；H,2.12；Cl,15.98；F,12.85；N,9.46.The above results Confirm that it is target product to obtain product.
Synthetic example 4：
The preparation of compound I-44
It is other to be carried out similarly instead in addition in synthetic example 1, being replaced other than compound F1-1 using compound F4-1 It answers, as a result obtains compound I-44 (4.43g, 30%).Mass spectrum m/z：Theoretical value：850.67；Measured value：852.51.Theoretical member Cellulose content (%) C44H20F10N8：C,62.12；H,2.37；F,22.33；N,13.17；Survey constituent content (%)：C,62.10； H,2.43；F,22.30；N,13.16.The above results confirm that it is target product to obtain product.
Synthetic example 5：
The preparation of compound I-54
It is other to be carried out similarly instead in addition in synthetic example 1, being replaced other than compound F1-1 using compound F5-1 It answers, as a result obtains compound I-54 (4.38g, 29%).Mass spectrum m/z：Theoretical value：870.66；Measured value：871.53.Theoretical member Cellulose content (%) C46H16F10N8：C,63.46；H,1.85；F,21.82；N,12.87；Survey constituent content (%)：C,63.43； H,1.92；F,21.80；N,12.85.The above results confirm that it is target product to obtain product.
Synthetic example 6：
The preparation of compound I-70
In addition in synthetic example 1, replacing compound F1-1, compound F6-2 to replace compound using compound F6-1 It is other to be carried out similarly reaction other than F1-2, as a result obtain compound I-70 (4.91g, 33%).Mass spectrum m/z：Theoretical value： 857.50；Measured value：859.75.Theoretical elemental content (%) C40H14Cl2F8N10：C,56.03；H,1.65；Cl,8.27；F, 17.72；N,16.33；Survey constituent content (%)：C,56.01；H,1.72；Cl,8.26；F,17.70；N,16.31.Above-mentioned knot Fruit confirms that it is target product to obtain product.
Synthetic example 7：
The preparation of compound I-105
In addition in synthetic example 1, replacing compound F1-1, compound F7-2 to replace compound using compound F7-1 It is other to be carried out similarly reaction other than F1-2, as a result obtain compound I-105 (3.59g, 27%).Mass spectrum m/z：Theoretical value： 766.67；Measured value：767.63.Theoretical elemental content (%) C42H18F4N12：C,65.80；H,2.37；F,9.91；N,21.92； Survey constituent content (%)：C,65.78；H,2.42；F,9.89；N,21.91.The above results confirm that obtain product produces for target Product.
Other target products with reference to shown in the synthetic method composite structure Formulas I of above-described embodiment 1-7.
Synthetic example 8：
The preparation of compound II-1
Under protection of argon gas, into flask be added compound E1-1 (14.0g, 150mmol), compound E1-2 (24.7g, 100mmol), sodium tert-butoxide (28.8g, 300mmol), tris(dibenzylideneacetone) dipalladium (1.4g, 1.5mmol), 1,1'- connection The bis- diphenyl phosphines of naphthalene -2,2'- (1.9g, 3mmol) and toluene (350ml) react 24 hours under conditions of 130 DEG C.It, will after cooling Mixture is filtered, and filtrate is concentrated under reduced pressure.The crude product of gained is subjected to column purification, is recrystallized with toluene, It after being filtered, is dried, as a result obtains intermediate Sub1-1 (22.3g, 86%).
Under protection of argon gas, into flask be added compound E1-3 (10g, 31mmol), compound E (11.1g, 31mmol), sodium tert-butoxide (3g, 31mmol), bis- (triphenylphosphine) palladium chlorides (II) (0.5g, 0.71mmol) and dimethylbenzene (500ml) reacts 24 hours under conditions of 130 DEG C.After cooling, water (1000ml) is added, mixture is filtered, will be filtered Liquid is extracted with toluene, and organic phase is dried with anhydrous magnesium sulfate.It is concentrated under reduced pressure, it is pure that the crude product of gained is carried out column Change, is recrystallized with toluene, after being filtered, be dried, as a result obtain intermediate Sub2-1 (10.5g, 61%).
Under protection of argon gas, into flask be added intermediate Sub1-1 (2.6g, 10mmol), intermediate Sub2-1 (5.5g, 10mmol), sodium tert-butoxide (1.3g, 13.5mmol), tris(dibenzylideneacetone) dipalladium (0.046g, 0.05mmol), three tertiary fourths Base phosphine (0.021g, 0.1mmol) and dehydrated toluene (50ml) react 2 hours at 80 DEG C.After cooling, water (500ml) is added, Mixture is filtered, filtrate is extracted with toluene, organic phase is dried with anhydrous magnesium sulfate.It is concentrated under reduced pressure, it will The crude product of gained carries out column purification, is recrystallized with toluene, after being filtered, is dried, as a result obtains product II-1 (5.1g, 70%).Mass spectrum m/z：Theoretical value：730.91；Measured value：731.83.Theoretical elemental content (%) C54H38N2O：C, 88.74；H,5.24；N,3.83；O,2.19；Survey constituent content (%)：C,88.72；H,5.31；N,3.81；O,2.16.It is above-mentioned As a result confirm that it is target product to obtain product.
Synthetic example 9：
The preparation of compound II-20
It is other to be carried out similarly instead in addition in synthetic example 8, being replaced other than compound E1-2 using compound E2-2 It answers, as a result obtains intermediate Sub1-2.
It is other to be carried out similarly instead in addition in synthetic example 8, being replaced other than compound E1-3 using compound E2-3 It answers, as a result obtains intermediate Sub2-2.
In addition in synthetic example 8, replacing intermediate Sub1-1 using intermediate Sub1-2, and use intermediate Sub2-2 is replaced other than intermediate Sub2-1, other to be carried out similarly reaction, as a result obtains product II-20 (5.3g, 75%).Matter Compose m/z：Theoretical value：704.87；Measured value：706.63.Theoretical elemental content (%) C52H36N2O：C,88.61；H,5.15；N, 3.97；O,2.27；Survey constituent content (%)：C,88.57；H,5.64；N,3.94；O,2.25.The above results confirmation is produced Object is target product.
Synthetic example 10：
The preparation of compound II-21
In addition in synthetic example 8, replacing compound E1-1 using compound E3-1, and replace using compound E3-2 It is other to be carried out similarly reaction other than compound E1-2, as a result obtain intermediate Sub1-3.
In addition in synthetic example 8, replaced other than intermediate Sub1-1 using intermediate Sub1-3, it is other similarly into Row reaction, as a result obtains product II-21 (6.0g, 72%).Mass spectrum m/z：Theoretical value：833.09；Measured value：835.23.It is theoretical Constituent content (%) C63H48N2：C,90.83；H,5.81；N,3.36；Survey constituent content (%)：C,90.81；H,5.85；N, 3.34.The above results confirm that it is target product to obtain product.
Synthetic example 11：
The preparation of compound II-26
It is other to be carried out similarly instead in addition in synthetic example 8, being replaced other than compound E1-3 using compound E4-3 It answers, as a result obtains intermediate Sub2-4.
In addition in synthetic example 8, replacing intermediate Sub1-1 using intermediate Sub1-3, and use intermediate Sub2-4 is replaced other than intermediate Sub2-1, other to be carried out similarly reaction, as a result obtains product II-26 (5.6g, 70%).Matter Compose m/z：Theoretical value：807.05；Measured value：808.53.Theoretical elemental content (%) C61H46N2：C,90.78；H,5.75；N, 3.47；Survey constituent content (%)：C,90.74；H,5.80；N,3.46.The above results confirm that it is target product to obtain product.
Synthetic example 12：
The preparation of compound II-29
It is other to be carried out similarly instead in addition in synthetic example 8, being replaced other than compound E1-3 using compound E5-3 It answers, as a result obtains intermediate Sub2-5.
In addition in synthetic example 8, replacing intermediate Sub1-1 using intermediate Sub1-3, and use intermediate Sub2-5 is replaced other than intermediate Sub2-1, other to be carried out similarly reaction, as a result obtains product II-29 (6.0g, 69%).Matter Compose m/z：Theoretical value：873.16；Measured value：875.32.Theoretical elemental content (%) C66H52N2：C,90.79；H,6.00；N, 3.21；Survey constituent content (%)：C,90.77；H,6.04；N,3.19.The above results confirm that it is target product to obtain product.
Synthetic example 13：
The preparation of compound II-57
It is other to be carried out similarly instead in addition in synthetic example 8, being replaced other than compound E1-2 using compound E6-2 It answers, as a result obtains intermediate Sub1-6.
In addition in synthetic example 8, replaced other than intermediate Sub1-1 using intermediate Sub1-6, it is other similarly into Row reaction, as a result obtains product II-57 (5.9g, 73%).Mass spectrum m/z：Theoretical value：806.03；Measured value：807.34.It is theoretical Constituent content (%) C60H43N3：C,89.41；H,5.38；N,5.21；Survey constituent content (%)：C,89.38；H,5.43；N, 5.19.The above results confirm that it is target product to obtain product.
Synthetic example 14：
The preparation of compound II-63
In addition in synthetic example 8, replacing compound E1-1 using compound E7-1, and replace using compound E7-2 It is other to be carried out similarly reaction other than compound E1-2, as a result obtain intermediate Sub1-7.
It is other to be carried out similarly instead in addition in synthetic example 8, being replaced other than compound E1-3 using compound E7-3 It answers, as a result obtains intermediate Sub2-7.
In addition in synthetic example 8, replacing intermediate Sub1-1 using intermediate Sub1-7, and use intermediate Sub2-7 is replaced other than intermediate Sub2-1, other to be carried out similarly reaction, as a result obtains product II-63 (5.9g, 73%).Matter Compose m/z：Theoretical value：779.99；Measured value：780.74.Theoretical elemental content (%) C58H41N3：C,89.31；H,5.30；N, 5.39；Survey constituent content (%)：C,89.29；H,5.35；N,5.37.The above results confirm that it is target product to obtain product.
Other target products with reference to shown in the synthetic method composite structure Formula II of above-described embodiment 8-14.
Application Example 1：The preparation of luminescent device 1
Selection ito glass is anode, is dried as in vacuum chamber after ultrasonic cleaning, is evacuated to 5 × 10-5Pa, above-mentioned Vacuum evaporation the compound of the present invention I-1 in anode grid substrate:Compound II-1=5mol%:95mol% as hole transmission layer, Evaporation thickness is 30nm.As luminescent material layer main body, 10% Firpic is used as to be mixed vacuum evaporation BND on the hole transport layer It is miscellaneous, evaporation thickness 30nm.The vacuum evaporation vacuum evaporation Alq on luminous material layer3As electron transfer layer, evaporation thickness is 30nm.Evaporating Al is as cathode, evaporation thickness 200nm on the electron transport layer.
Application Example 2：The preparation of luminescent device 2
Change the compound I-1 in Application Example 1 into compound I-18, compound II-1 changes compound II-20 into.
Application Example 3：The preparation of luminescent device 3
Change the compound I-1 in Application Example 1 into compound I-22, compound II-1 changes compound II-21 into.
Application Example 4：The preparation of luminescent device 4
Change the compound I-1 in Application Example 1 into compound I-44, compound II-1 changes compound II-26 into.
Application Example 5：The preparation of luminescent device 5
Change the compound I-1 in Application Example 1 into compound I-54, compound II-1 changes compound II-29 into.
Application Example 6：The preparation of luminescent device 6
Change the compound I-1 in Application Example 1 into compound I-70, compound II-1 changes compound II-57 into.
Application Example 7：The preparation of luminescent device 7
Change the compound I-1 in Application Example 1 into compound I-105, compound II-1 changes compound II-63 into.
Comparative example 1
Selection ito glass is anode, is dried as in vacuum chamber after ultrasonic cleaning, is evacuated to 5 × 10-5Pa, above-mentioned Vacuum evaporation NPB is as hole transmission layer, evaporation thickness 30nm in anode grid substrate.Vacuum evaporation BND on the hole transport layer As luminescent material layer main body, 10% Firpic is as doping, evaporation thickness 30nm.The vacuum evaporation on luminous material layer Vacuum evaporation Alq3As electron transfer layer, evaporation thickness 30nm.For evaporating Al as cathode, vapor deposition is thick on the electron transport layer Degree is 200nm.
The characteristics of luminescence test result of luminescent device prepared by Application Example 1-7 of the present invention and comparative example 1 is such as Shown in table 1.
Table 1
From table 1 it follows that the dopant material of the present invention is applied to organic electroluminescence as hole mobile material In part, which shows lower driving voltage, higher luminous efficiency and longer service life, and And there is preferable durability and reliability.

Claims (10)

1. a kind of dopant material, which is characterized in that including dopant and host material, the dopant has shown in structural formula I General structure：
Wherein, the R1、R2Independent fat-based selected from substituted or unsubstituted C1~C15, substituted or unsubstituted C6~ The aryl of C60, substituted or unsubstituted C3~C60 heteroaryl in one kind；The R3、R4、R5、R6It is independent selected from cyano, Halogen, trifluoromethyl, trifluoromethoxy, nitro, the fat-based of substituted or unsubstituted C1~C60, substituted or unsubstituted C6 The aryl of~C60, substituted or unsubstituted C3~C60 heteroaryl in one kind；The Ar7、Ar8It is independent selected from substitution or The heteroaryl of the fat-based of unsubstituted C1-C12, the aryl of substituted or unsubstituted C6~C60, substituted or unsubstituted C3~C60 One kind in base；
The wherein described host material has general structure shown in formula II：
The X is selected from C (R)2、NR、P(O)R、PR、S、SO、SO2、Si(R)2, one kind in O, wherein R is selected from substitution or unsubstituted The alkyl of C1~C15, the aryl of substituted or unsubstituted C6~C24, substituted or unsubstituted C3~C24 heteroaryl in It is a kind of；
The A is hydrogen, condense the aryl of substituted or unsubstituted C6~C60 on phenyl ring, condense substitution on phenyl ring or One kind in the heteroaryl of unsubstituted C3~C60；The Ar1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted C6~C60 Aryl, substituted or unsubstituted C3~C60 heteroaryl in one kind.
2. a kind of dopant material according to claim 1, which is characterized in that
Ar in the structural formula I7、Ar8Independently selected from the aryl, substituted or unsubstituted of substituted or unsubstituted C6-C12 The heteroaryl of C3-C12；
X in the formula II is selected from C (R)2、NR、S、Si(R)2, one kind in O, wherein R is selected from substituted or unsubstituted C1 The alkyl of~C10, the aryl of substituted or unsubstituted C6~C18, substituted or unsubstituted C3~C18 heteroaryl in one Kind；The A is hydrogen, condense the aryl of substituted or unsubstituted C6~C30 on phenyl ring, condenses substitution on phenyl ring or not One kind in the heteroaryl of substituted C3~C30；The Ar1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted C6~C30's Aryl, substituted or unsubstituted C3~C30 heteroaryl in one kind.
3. a kind of dopant material according to claim 1, which is characterized in that
Ar in the structural formula I7、Ar8Selected from phenyl；
X in the formula II is selected from C (R)2, one kind in NR, S, O, wherein R is selected from substituted or unsubstituted C1~C8's Alkyl, the aryl of substituted or unsubstituted C6~C12, substituted or unsubstituted C3~C12 heteroaryl in one kind；The A For hydrogen, the heteroaryl of the aryl for condensing substituted or unsubstituted C6~C18 on phenyl ring, substituted or unsubstituted C6~C18 In one kind；The Ar1、Ar2、Ar3Independent aryl, substituted or unsubstituted C3 selected from substituted or unsubstituted C6~C18 One kind in the heteroaryl of~C18.
4. a kind of dopant material according to claim 1, which is characterized in that
R in the structural formula I3、R4、R5、R6Hydrogen on cyano, C is all by halogen, cyano, trifluoromethyl, three The heteroaryl for the C3-C30 that the aryl of C6-C30 or the hydrogen on C of fluorine methoxyl group substitution are all replaced by halogen, cyano, trifluoromethyl Base；
X in the formula II is selected from C (R)2、NR、S、Si(R)2, one kind in O, wherein R it is independent selected from methyl, ethyl, Propyl, isopropyl, butyl, tertiary butyl, benzyl, phenethyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridine Base, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazine radical, substitution do not take The furyl in generation, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrole radicals.
5. a kind of dopant material according to claim 1, which is characterized in that
R in the structural formula I3、R4、R5、R6Independently selected from cyano or following group：
Wherein, Z1、Z2、Z3、Z4、Z5、Z6、Z7Independently selected from halogen, cyano, trifluoromethyl, trifluoromethoxy；
A in the formula II is selected from hydrogen, substituted or unsubstituted phenyl.
6. a kind of dopant material according to claim 1, which is characterized in that
R in the structural formula I3With R4It is asynchronously cyano, but at least one is cyano；R5With R6It is asynchronously cyano, but At least one is cyano；
Ar in the formula II1、Ar2、Ar3It is independent to be selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl Base, substituted or unsubstituted naphthalene, substituted or unsubstituted terphenyl, substituted or unsubstituted carbazyl, substitution do not take The anthryl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted triphenylene, substitution or Two fluorenyl of unsubstituted spiral shell, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted furans Base, substituted or unsubstituted thienyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofurans Base, substituted or unsubstituted quinolyl.
7. a kind of dopant material according to claim 1, which is characterized in that the R in the structural formula I1、R2Independently select From methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tertiary butyl, isobutyl group or following group：
Wherein, X1、X2、X3、X4、X5、X6、X7、X8、X9Independently selected from hydrogen, halogen, cyano, trifluoromethyl, trifluoromethoxy, The alkyl of C1-C4, the alkoxy of C1-C4；Y is selected from fat-based, the aryl of C6-C12 or the heteroaryl of C3-C12 of C1-C4.
8. a kind of dopant material according to claim 1, which is characterized in that
The one kind of the dopant of the structural formula I in chemical constitution as follows：
9. a kind of dopant material according to claim 1, which is characterized in that
The one kind of the host material of the formula II in chemical constitution as follows：
10. a kind of organic electroluminescence device, which is characterized in that the organic matter layer includes hole transmission layer, and the hole passes Defeated layer includes a kind of dopant material described in any one of claim 1-9.
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CN108821985A (en) * 2018-06-01 2018-11-16 长春海谱润斯科技有限公司 A kind of aromatic amine derivant and its organic electroluminescence device
CN108822020A (en) * 2018-06-04 2018-11-16 长春海谱润斯科技有限公司 A kind of benzidine derivative and its organic electroluminescence device
CN109400520A (en) * 2018-11-27 2019-03-01 长春海谱润斯科技有限公司 A kind of benzidine compound and its organic electroluminescence device
CN110903235A (en) * 2019-12-05 2020-03-24 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound and preparation method and application thereof
CN113461693A (en) * 2021-06-30 2021-10-01 上海天马微电子有限公司 Organic compound, hole injection material and application thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108821985A (en) * 2018-06-01 2018-11-16 长春海谱润斯科技有限公司 A kind of aromatic amine derivant and its organic electroluminescence device
CN108821985B (en) * 2018-06-01 2021-05-11 长春海谱润斯科技股份有限公司 Aromatic amine derivative and organic electroluminescent device thereof
CN108822020A (en) * 2018-06-04 2018-11-16 长春海谱润斯科技有限公司 A kind of benzidine derivative and its organic electroluminescence device
CN109400520A (en) * 2018-11-27 2019-03-01 长春海谱润斯科技有限公司 A kind of benzidine compound and its organic electroluminescence device
CN110903235A (en) * 2019-12-05 2020-03-24 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound and preparation method and application thereof
CN110903235B (en) * 2019-12-05 2022-12-27 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound and preparation method and application thereof
CN113461693A (en) * 2021-06-30 2021-10-01 上海天马微电子有限公司 Organic compound, hole injection material and application thereof

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