CN107833974A - A kind of novel electroluminescent device - Google Patents

A kind of novel electroluminescent device Download PDF

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CN107833974A
CN107833974A CN201710565557.3A CN201710565557A CN107833974A CN 107833974 A CN107833974 A CN 107833974A CN 201710565557 A CN201710565557 A CN 201710565557A CN 107833974 A CN107833974 A CN 107833974A
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CN107833974B (en
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邢其锋
李之洋
刘叔尧
任雪艳
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Guan Eternal Material Technology Co Ltd
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Abstract

The invention discloses a kind of organic electroluminescence device, including first electrode, second electrode and one or more layers organic layer between the first electrode and second electrode, luminescent layer and electron transfer layer are comprised at least in the organic layer, it is characterised in that：The electron transfer layer thickness is 5 100nm, and at least one is included in electron transfer layer as the compound shown in formula (I)：Wherein, L is selected from chemical bond, C6~C12Arlydene or sub- condensed-nuclei aromatics group, C3~C12Inferior heteroaryl or sub- condensed hetero ring aromatic hydrocarbon group；Ar1、Ar2And Ar3It is respectively and independently selected from C6~C30Substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C30Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C10Alkylidene, halogen, cyano group, nitro, C6~C30Substituted or unsubstituted aryl or condensed-nuclei aromatics group, C3~C30Substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, R3With R4Between can be interconnected to form cyclic structure.The organic electroluminescence device of the present invention has the advantages of operating voltage is low and luminous efficiency is high.

Description

A kind of novel electroluminescent device
Technical field
The invention belongs to field of organic electroluminescence, it is more particularly related to a kind of novel electroluminescent Device, using a kind of new general formula compound as electron transport layer materials in the device.
Background technology
Display of organic electroluminescence (hereinafter referred to as OLED) has from main light emission, low-voltage direct-current driving, all solidstate, regarded Angular width, in light weight, composition and a series of advantages such as technique is simple, compared with liquid crystal display, display of organic electroluminescence Backlight is not needed, visual angle is big, and power is low, and up to 1000 times of liquid crystal display, its manufacturing cost is but less than its response speed The liquid crystal display of equal resolution ratio, therefore, organic electroluminescence device has broad application prospects.
As OLED technology is illuminating and shown the continuous propulsion in two big fields, people are for influenceing OLED performance The research of efficient organic material focuses more on, the organic electroluminescence device of an excellent in efficiency long lifespan be typically device architecture with The result of the optimization collocation of various organic materials.In most common OLED structure, the organic of following species is generally included Material：Hole-injecting material, hole mobile material, electron transport material, and assorted luminescent material (dyestuff or doping visitor Body material) and corresponding material of main part etc..
The electron transport material that tradition uses in electroluminescent device is Alq3, but Alq3 electron mobility is than relatively low (about in 10-6cm2/Vs).In order to improve the electronic transmission performance of electroluminescence device, researcher has done substantial amounts of exploration Research work.LG chemistry reports a series of derivative of pyrenes in the patent specification of China, is used as in electroluminescence device Electric transmission and injection material, improve the luminous efficiency (publication number CN 101003508A) of device.Cao Yong et al. synthesizes FFF-Blm4(J.Am.Chem.Soc.；(Communication)；2008；130(11)；3282-3283) as electric transmission and Layer material (compared with Ba/Al and individually by the use of Al as negative electrode) is injected, significantly improves electron injection and the transmission of device, Improve electroluminescence efficiency.Kodak is at United States Patent (USP) (publication number US 2006/0204784 and US 2007/0048545) In, mixed electronic transport layer is mentioned, using a kind of material of low lumo energy and the electric transmission material of another low bright voltage The doping such as material and other materials such as metal material forms.
Preferable electron transport material, it should which there is the characteristic of following several respects：With reversible electrochemical reducting reaction； HOMO and lumo energy are suitable；Electron mobility is high；Good film-forming property；Tg is high；It is preferably able to stop hole.From compound structure side Face, it is desirable to which molecule contains electron deficient construction unit, receives electronic capability with good；Molecular weight is sufficiently large, ensure have compared with High Tg, so as to have good heat endurance, while molecular weight can not be too big, in favor of vacuum evaporation film forming.
The electron transport material performance being currently known is unsatisfactory, and industry is still badly in need of developing new electron transport material.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of operating voltage is low, luminous efficiency is high, the Organic Electricity of long lifespan Electroluminescence device.Such novel electroluminescent device has selected a kind of new electron transport material.
Another technical problems to be solved of the invention are to provide a kind of new general formula compound of good performance.
To solve the above problems, the invention provides a kind of organic electroluminescence device, including first electrode, second electrode And one or more layers organic layer between the first electrode and second electrode, luminescent layer is comprised at least in the organic layer At least one is included and electron transfer layer, the electron transfer layer thickness are 5-100nm, and in electron transfer layer by formula (I) Shown compound：
Wherein, L is selected from chemical bond, C6~C12Arlydene or sub- condensed-nuclei aromatics group, C3~C12Inferior heteroaryl or Asia Condensed hetero ring aromatic hydrocarbon group；
Wherein, Ar1、Ar2And Ar3It is respectively and independently selected from C6~C30Substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C30Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group.Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted When aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituted radical thereon is independently selected from halogen, cyanogen Base, nitro, or selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~C6Alkoxy or thio alkoxy group, Huo Zhexuan From Si (R5)3, the R5Selected from C1~C6Alkyl.
Wherein, R1、R2、R3、R4It is respectively and independently selected from hydrogen, C1~C10Alkylidene, halogen, cyano group, nitro, C6~C30's Substituted or unsubstituted aryl or condensed-nuclei aromatics group, C3~C30Substituted or unsubstituted heteroaryl or condensed hetero ring aryl Group.Work as R1、R2、R3、R4When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, The substituted radical thereon is independently selected from halogen, cyano group, nitro, or selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~ C6Alkoxy or thio alkoxy group, or selected from Si (R5)3, the R5Selected from C1~C6Alkyl.
Further, the R3With R4Between when can be interconnected to form cyclic structure, such ring structure can be fat Fat race is monocyclic or polycyclic, aromatic monocyclic or condensed ring, and hetero atom can be included in these rings, wherein, as aliphatic monocyclic Example, for example, R3With R4Two groups of middle arbitrary neighborhood connect to form aliphatic five-membered ring, hexatomic ring, the structure of these rings Hetero atom is can also be in addition to carbon atom into atom, these rings there can be substituent, and the carbon atom for forming ring can also Form ketone group.As the example of these rings, pentamethylene ring, cyclohexane ring, dicyclopentenyl ring, nafoxidine ring, tetrahydrochysene can be enumerated Ester ring that carbon atom in furan nucleus, piperidine ring and pentamethylene ring and cyclohexane ring substitutes to obtain by ketone group etc..As fragrance The monocyclic or condensed ring of race, preferably C6~C30 monocyclic or condensed ring, can enumerate phenyl ring, naphthalene nucleus etc. as an example；As comprising miscellaneous Monocyclic or polycyclic, preferably pyrrole ring, benzopyrrole ring, pyridine ring, indole ring, N- phenyl substituted indoles ring, the thiophene of atom Fen ring, benzothiophene ring, furan nucleus, benzofuran ring etc..
Specifically, as the above-mentioned Ar of definition1、Ar2And Ar3With R1、R2、R3And R4When being respectively and independently selected from aryl, refer to be selected from Aromatics ring system with certain amount ring skeleton carbon atom, including single ring architecture substituted radical also include covalent such as phenyl The aromatic ring substituents of attachment structure are rolled into a ball such as xenyl, terphenyl.
Further, in organic electroluminescence device of the invention, in the logical formula (I) as electron transport layer materials, Ar1、Ar2And Ar3Independently it preferably is selected from C6~C20Substituted aryl or condensed-nuclei aromatics group, C5~C20Substitution or non-take The heteroaryl or condensed hetero ring aromatic hydrocarbon group in generation.
Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aryl During group, the substituted radical thereon, which is independently selected from, preferably is selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, Ar is worked as1、Ar2And Ar3It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl During group, the hetero atom is preferably one or more O, S and N.
Further, in organic electroluminescence device of the invention, in the logical formula (I) as electron transport layer materials, Ar1、Ar2And Ar3It can be the same or different, preferably Ar1、Ar2And Ar3It is different.
Further, in organic electroluminescence device of the invention, in the logical formula (I) as electron transport layer materials, Ar1、Ar2And Ar3Independently preferable aryl or fused ring aryl group include：Phenyl, xenyl, terphenyl, naphthyl, anthracene Base, phenanthryl, indenyl, fluoranthene base, Sanya phenyl, pyrenyl, base,Base or aphthacene base；By furyl, thienyl, pyrrole radicals And/or the phenyl of pyridine radicals substitution；2- xenyls, 3- xenyls, 4- xenyls, p- terphenyl -4- bases, p- terphenyl Base -3- bases, p- terphenyl -2- bases, m- terphenyl -4- bases, m- terphenyl -3- bases and m- terphenyl -2- bases. Benzene binaphthyl, 4- naphthylphenyls, 6- phenyl napthyls, 7- phenyl phenanthryl.
In the group that above-mentioned naphthyl is made up of 1- naphthyls and 2- naphthyls；The anthryl is selected from by 1- anthryls, 2- anthryls and 9- In the group that anthryl is formed；The fluorenyl is selected from the group being made up of 1- fluorenyls, 2- fluorenyls, 3- fluorenyls, 4- fluorenyls and 9- fluorenyls In；The fluorenyl derivative is selected from by 9,9 '-dimethyl fluorene, and 9, in the group that the fluorenes of 9 '-spiral shell two and benzfluorene are formed；The pyrenyl In the group being made up of 1- pyrenyls, 2- pyrenyls and 4- pyrenyls；The aphthacene base is selected from by 1- aphthacenes base, 2- aphthacenes In the group that base and 9- aphthacene bases are formed.
Further, in formula (I), Ar1、Ar2And Ar3Independently preferable heteroaryl groups include：Furyl, phenyl Furyl, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, fluorenyl, indeno Fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, Benzoquinoline, dibenzofuran group, dibenzothiophenes base, dibenzopyrrole base, carbazyl and its derivative, the two of phenyl substitution At least one of azoles, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group, wherein, the carbazyl derives Thing can include but is not limited in 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole and indolocarbazole extremely Few one kind.
Further, in organic electroluminescence device of the invention, in the logical formula (I) as electron transport layer materials, R1、 R2、R3And R4Independently it preferably is selected from hydrogen, C1~C5Alkylidene, halogen, cyano group, nitro, C6~C15It is substituted or unsubstituted Aryl or condensed-nuclei aromatics group, C3~C15Substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group.
Work as R1、R2、R3And R4It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aryl During group, the substituted radical thereon, which is independently selected from, preferably is selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, R is worked as1、R2、R3And R4It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl During group, the hetero atom is preferably one or more O, S and N.
Further, in formula (I), R1、R2、R3And R4It is respectively and independently selected from following radicals：Methyl, ethyl, isopropyl, The tert-butyl group, cyclopenta, cyclohexyl, cyano group, nitro, benzene (I) base, naphthyl, Sanya phenyl, 9,9 dimethyl fluorenes, the fluorenyl of spiral shell two, furan Mutter base, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, Fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran Base, indyl, benzoquinoline, dibenzofuran group, dibenzothiophenes base, dibenzopyrrole base, carbazyl and its derivative, benzene At least one of diazole, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group of base substitution, wherein, it is described Carbazole radical derivative can include but is not limited to 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole and indoles simultaneously At least one of carbazole.
Further, organic electroluminescence device of the invention, the thickness of preferably described luminescent layer is 5nm to 50nm, more The thickness of preferable luminescent layer is 10nm to 30nm.It is preferred that its electron transfer layer thickness is 5-100nm, more preferably electric transmission Thickness degree is 10-40nm.
Further, in organic electroluminescence device of the invention, two kinds of compounds can be included in electron transfer layer, One kind is as the compound shown in formula (I), and another electron transport material is preferably LiQ, the doping weight of both compounds Ratio is 90:10 to 10:90.
Further, the preferred example as organic electroluminescence device of the invention, can enumerate from following representatives Organic electroluminescence devices of the property compound A1~A27 as electron transport layer materials.
The present invention organic electroluminescence device possess excellent photoelectricity performance, have relatively low device rise it is bright and Operating voltage, while there is of a relatively high device efficiency, and device lasts a long time.
There is the structure shown in below formula (I) present invention simultaneously provides a kind of new quinazoline substitution anthracene derivant：
Wherein, L is selected from chemical bond, C6~C12Arlydene or sub- condensed-nuclei aromatics group, C3~C12Inferior heteroaryl or Asia Condensed hetero ring aromatic hydrocarbon group；
Wherein, Ar1、Ar2And Ar3It is respectively and independently selected from C6~C30Substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C30Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group.Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted When aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, the substituted radical thereon is independently selected from halogen, cyanogen Base, nitro, or selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~C6Alkoxy or thio alkoxy group, Huo Zhexuan From Si (R5)3, the R5Selected from C1~C6Alkyl.
Wherein, R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C10Alkylidene, halogen, cyano group, nitro, C6~C30's Substituted or unsubstituted aryl or condensed-nuclei aromatics group, C3~C30Substituted or unsubstituted heteroaryl or condensed hetero ring aryl Group.Work as R1、R2、R3And R4When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, The substituted radical thereon is independently selected from halogen, cyano group, nitro, or selected from C1~C30Alkyl or cycloalkyl, alkenyl, C1~ C6Alkoxy or thio alkoxy group, or selected from Si (R5)3, the R5Selected from C1~C6Alkyl.
Specifically, as the above-mentioned R of definition3With R4Between when can be interconnected to form cyclic structure, such ring structure can be with It is aliphatic monocyclic or polycyclic, aromatic monocyclic or condensed ring, hetero atom can be included in these rings, wherein, as aliphatic Monocyclic example, for example, R3With R4Two groups of middle arbitrary neighborhood connect to form aliphatic five-membered ring, hexatomic ring, these rings Constituting atom hetero atom is can also be in addition to carbon atom, these rings can have substituent, form the carbon atom of ring Ketone group can be formed.As the example of these rings, can enumerate pentamethylene ring, cyclohexane ring, dicyclopentenyl ring, nafoxidine ring, Ester ring that carbon atom in tetrahydrofuran ring, piperidine ring and pentamethylene ring and cyclohexane ring substitutes to obtain by ketone group etc..As The monocyclic or condensed ring of aromatic monocyclic or condensed ring, preferably C6~C30, can enumerate phenyl ring, naphthalene nucleus etc. as an example；As bag Containing heteroatomic monocyclic or polycyclic, preferably pyrrole ring, benzopyrrole ring, pyridine ring, indole ring, N- phenyl substituted indoles Ring, thiphene ring, benzothiophene ring, furan nucleus, benzofuran ring etc..
Specifically, as the above-mentioned Ar of definition1、Ar2And Ar3With R1、R2、R3And R4When being respectively and independently selected from aryl, refer to be selected from Aromatics ring system with certain amount ring skeleton carbon atom, including single ring architecture substituted radical also include covalent such as phenyl The aromatic ring substituents of attachment structure are rolled into a ball such as xenyl, terphenyl.
Specifically, as the above-mentioned Ar of definition1、Ar2And Ar3With R1、R2、R3And R4It is when being respectively and independently selected from condensed-nuclei aromatics group Refer to the aromatics ring system with certain amount ring skeleton carbon atom, including condensed cyclic structure substituted radical also wraps such as naphthyl, anthryl Include building stone such as benzene binaphthyl, naphthalene xenyl, the biphenyl connection that condensed cyclic structure substituted radical is connected with single ring architecture aryl Anthryl etc., in addition to the thick aromatic ring substituents group of structure is covalently attached such as binaphthyl.
Specifically, as the above-mentioned Ar of definition1、Ar2And Ar3With R1、R2、R3And R4It is respectively and independently selected from heteroaryl or condensed hetero ring virtue Refer to that including one or more is selected from B, N, O, S, P (=O), Si and P hetero atom and the list with ring carbon atom during hydrocarbyl group Ring or fused ring aryl.
Further, in formula (I), Ar1、Ar2And Ar3Independently it preferably is selected from C6~C20Substituted aryl or condensed ring virtue Hydrocarbyl group, C5~C20Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group.
Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aryl During group, the substituted radical thereon, which is independently selected from, preferably is selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, Ar is worked as1、Ar2And Ar3It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl During group, the hetero atom is preferably one or more O, S and N.
Further, Ar1、Ar2And Ar3It can be the same or different, preferably Ar1、Ar2And Ar3It is different.
Further, in formula (I), Ar1、Ar2And Ar3Independently preferable aryl or fused ring aryl group include：Benzene Base, xenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluoranthene base, Sanya phenyl, pyrenyl, base,Base or aphthacene Base；The phenyl substituted by furyl, thienyl, pyrrole radicals and/or pyridine radicals；It is 2- xenyls, 3- xenyls, 4- xenyls, p- Terphenyl -4- bases, p- terphenyl -3- bases, p- terphenyl -2- bases, m- terphenyl -4- bases, m- terphenyl - 3- bases and m- terphenyl -2- bases.Benzene binaphthyl, 4- naphthylphenyls, 6- phenyl napthyls, 7- phenyl phenanthryl.
In the group that above-mentioned naphthyl is made up of 1- naphthyls and 2- naphthyls；The anthryl is selected from by 1- anthryls, 2- anthryls and 9- In the group that anthryl is formed；The fluorenyl is selected from the group being made up of 1- fluorenyls, 2- fluorenyls, 3- fluorenyls, 4- fluorenyls and 9- fluorenyls In；The fluorenyl derivative is selected from by 9,9 '-dimethyl fluorene, and 9, in the group that the fluorenes of 9 '-spiral shell two and benzfluorene are formed；The pyrenyl In the group being made up of 1- pyrenyls, 2- pyrenyls and 4- pyrenyls；The aphthacene base is selected from by 1- aphthacenes base, 2- aphthacenes In the group that base and 9- aphthacene bases are formed.
Further, in formula (I), Ar1、Ar2And Ar3Independently preferable heteroaryl groups include：Furyl, phenyl Furyl, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, fluorenyl, indeno Fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, Benzoquinoline, dibenzofuran group, dibenzothiophenes base, dibenzopyrrole base, carbazyl and its derivative, the two of phenyl substitution At least one of azoles, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group, wherein, the carbazyl derives Thing can include but is not limited in 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole and indolocarbazole extremely Few one kind.
Further, in formula (I), R1、R2、R3And R4Independently it preferably is selected from hydrogen, C1~C5Alkylidene, halogen, cyano group, Nitro, C6~C15Substituted or unsubstituted aryl or condensed-nuclei aromatics group, C3~C15Substituted or unsubstituted heteroaryl or Condensed hetero ring aromatic hydrocarbon group.
Work as R1、R2、R3And R4It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aryl During group, the substituted radical thereon, which is independently selected from, preferably is selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, R is worked as1、R2、R3And R4It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl During group, the hetero atom is preferably one or more O, S and N.
Further, in formula (I), R1、R2、R3And R4It is respectively and independently selected from following radicals：Methyl, ethyl, isopropyl, The tert-butyl group, cyclopenta, cyclohexyl, cyano group, nitro, benzene (I) base, naphthyl, Sanya phenyl, 9,9 dimethyl fluorenes, the fluorenyl of spiral shell two, furan Mutter base, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, Fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran Base, indyl, benzoquinoline, dibenzofuran group, dibenzothiophenes base, dibenzopyrrole base, carbazyl and its derivative, benzene At least one of diazole, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group of base substitution, wherein, it is described Carbazole radical derivative can include but is not limited to 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole and indoles simultaneously At least one of carbazole.
The molecular weight of the quinazoline substitution anthracene compound of the present invention is preferably less than 1000, and more preferably 450~900, More preferably 600~800, so suitable molecular size range, all offered convenience to the synthesis of compound, dissolving, evaporation, And luminescent properties are more preferable.
Further, in logical formula (I) of the invention, following concrete structure compounds can preferably be gone out：A1-A27, these changes Compound is only representational.
The advantages of organic electroluminescence device of the present invention, is：
Electron transport layer materials in device select above-mentioned such general formula compound, can preferably with luminous layer main body The lumo energy of material matches, and so as to effectively reduce device operating voltages and improve device light emitting efficiency, extends device In the life-span, there is very important practical significance in the manufacture of organic electroluminescence device.
The advantages of the compounds of this invention, is：
1st, the compounds of this invention structure design substitutes anthracene structure to be so designed to as parent nucleus group from single quinazoline Protect parent nucleus active site, to keep compound stability there is positive effect, while may insure Cloud Distribution in On parent nucleus, LUMO distributions are consistent with Cloud Distribution；Its molecular weight of the compounds of this invention is smaller, can be real at a lower temperature The sublimation purification and element manufacturing of existing material, be advantageous to the stability of material；
2nd, the precursor structure of the compounds of this invention has coplanarity well, and there is its derivative higher carrier to pass Defeated property, so as to significantly reduce the operating voltage of the device using such material, while compound possesses the high migration having Rate also makes the thickness control of material have broader adjusting range, and the work of device can not be significantly affected by increasing the thickness of material Make voltage；
3rd, the precursor structure of the compounds of this invention has deeper LUMO, realizes the performance of good transmission electronics, together When keep coplanar structure to be advantageous to the film forming of molecule；Substitute the change of ground level and electronic property, can finely tune most The energy level and transmission performance of whole target compound, such compound are used as electron transport layer materials, can significantly increased The luminous efficiency of device；
Brief description of the drawings
From the detailed description to the embodiment of the present invention below in conjunction with the accompanying drawings, of the invention these and/or other side and Advantage will become clearer and be easier to understand, wherein：
Fig. 1 is the compounds of this invention A1 highest occupied molecular orbital (HOMO)；
Fig. 2 is the compounds of this invention A1 lowest unoccupied molecular orbital (LUMO)；
Fig. 3 is the compounds of this invention A5 highest occupied molecular orbital HOMO；
Fig. 4 is the compounds of this invention A5 lowest unoccupied molecular orbital LUMO.
Embodiment
Below with reference to following examples set forth the preparation method of the representation compound of the present invention.Due to the compounds of this invention With identical skeleton, those skilled in the art are based on these preparation methods, can by known functional group's conversion method, readily Synthesize other compounds of the invention.Hereinafter, the preparation method and photism of the luminescent device comprising the compound are also provided Matter determines.
Synthetic example：
Preparation is simple for the compounds of this invention, and raw material is easy to get, and is suitable for volume production amplification.
In synthetic example various chemicals used for example petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, Dichloromethane, carbon tetrachloride, acetone, 1,2- double (bromomethyl) benzene, CuI, o-phthaloyl chloride, phenylhydrazine hydrochloride, trifluoroacetic acid, second Sour, trans-diaminocyclohexane, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-Fluorenone, the tert-butyl alcohol The bromo- 2- methyl naphthalenes of sodium, Loprazolam, 1-, o-dibromobenzene, butyl lithium, Bromofume, o-dibromobenzene, benzoyl peroxide, 1- (2- bromophenyls) -2- methyl naphthalenes, N- bromo-succinimides, methoxyl methyl San Jia Ji phosphonium chlorides, three (dibenzalacetones) two Palladium, tetrakis triphenylphosphine palladium, 1,3- pairs of 2-phenyl-phosphine oxide nickel chloride, carbazole, 3,6- Dimethylcarbazoles, 3- (2- naphthyls) -6- The bases such as phenyl carbazole, N- phenyl carbazole -3- boric acid, 9- (2- naphthyls) carbazole -3- boric acid, the bromo- 2,5- diaminobenzenes of 1,4- bis- Industrial chemicals chemical products can be commercially available at home.The compound for the synthetic method do not mentioned in the present invention all passes through The raw produce that commercial sources obtain.
The analysis detection of intermediate and compound in the present invention uses AB SCIEX mass spectrographs (4000QTRAP) and cloth Shandong Gram NMR (400M).
The compound A1 of synthetic example 1. synthesis
Under nitrogen protection, 2- bromo anthraquinones M1 (26.5g, 0.01mol), pinacol borate (0.015mol), Pd (dppf) Cl2 (1%), potassium carbonate mixing are dissolved in 500ml toluene, are heated to flowing back, and reaction overnight, reaction solution column chromatography, concentrates, petroleum ether Boil and wash, obtain intermediate M2 (20.1g, yield 89.6%).
Under nitrogen protection, to equipped with mechanical agitation, 4- benzene is added in intermediate M2 (6.7g, 22mmol, 1.1eq) there-necked flask Base -2- chloropyrazines (1eq.), potassium carbonate 5eq, Pd (Pph3) 4 (2%), toluene 1000ml+ ethanol 500ml+300ml water, open Stirring, is heated to flowing back, and reacts 8h.Organic phase silica gel column chromatography, concentration, with re crystallization from toluene obtain yellow powder M3 (9.0g, 93.7%).
Under nitrogen protection, (25mmol) 2- bromonaphthalenes are dissolved in tetrahydrofuran, and ice ethanol bath is down to -78 DEG C, and n-BuLi is added dropwise Solution, cryogenic conditions are kept, is added dropwise, temperature control 30min, intermediate M3 (4.8g, 10mmol) is dissolved in tetrahydrofuran, be added dropwise Enter in reaction bulb, be added dropwise, heat up naturally, react 8h.Watery hydrochloric acid is added in reaction solution, is extracted with ethyl acetate, organic phase Concentration, solid separate out, and are filtrated to get intermediate M4 (4.8g, 93.1%).
Intermediate M4 (5.1g, 10mmol), add in reaction bulb, add 100ml glacial acetic acid, add KI (20mmol), hypophosphorous acid hydrogen sodium (20mmol) is added, is heated to flowing back, react 5h.Filtering, with water, ethanol rinse, collection obtains Yellow powder A1 (5.3g, 79.1%).
Compound A1 magnetic resonance spectroscopy data：
1H NMR(400MHz,Chloroform)δ8.40(s,2H),8.33(s,3H),7.75(s,3H),
7.55 (s, 4H), 7.48 (t, J=28.0Hz, 10H), 7.24 (d, J=4.0Hz, 8H)
The compound A2 of synthetic example 2. synthesis
Synthesis step is the 4- (2- naphthyls) that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A1, difference Pyrazine, after reaction terminates, isolated white solid 6.2g.
Compound A2 magnetic resonance spectroscopy data：
1H NMR (400MHz, Chloroform) δ 8.86 (s, 1H), 8.33 (d, J=12.0Hz, 2H),
8.20 (s, 1H), 8.08 (d, J=12.0Hz, 2H), 7.99 (s, 1H), 7.63 (s, 1H), 7.57 (d, J= 12.0Hz,2H),7.38(s,2H),7.14(s,1H),6.90(s,1H).
The synthesis of the compound A-13 of synthetic example 3.
Synthesis step is the 2- phenyl -4- chlorine that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A1, difference Pyrazine, after reaction terminates, isolated white solid 6.4.
1H NMR (400MHz, Chloroform) δ 9.11 (s, 2H), 8.90 (s, 2H), 8.31 (d, J=12.0Hz, 50H), 7.86 (dd, J=8.0,59.0Hz, 6H), 7.65 (s, 1H), 7.65 (s, 2H), 7.62 (s,
4H),7.55(s,2H),7.49(s,2H),7.41(s,1H).
The compound A4 of synthetic example 4. synthesis
Synthesis step is 2, the 6- dibromo-anthraquinones that 2- bromo anthraquinones are replaced with to equivalent, obtained with compound A1, difference Intermediate M2B 4.6g.
Under nitrogen protection, to equipped with mechanical agitation, 4- is added in intermediate M2B (6.7g, 22mmol, 1.1eq) there-necked flask Phenyl -2- chloropyrazines (1eq.), potassium carbonate 5eq, Pd (Pph3) 4 (2%), toluene 1000ml+ ethanol 500ml+300ml water, open Stirring is opened, is heated to flowing back, reacts 8h.Organic phase silica gel column chromatography, concentration, yellow powder M3B is obtained with re crystallization from toluene (9.0g, 93.7%).
Under nitrogen protection, to equipped with mechanical agitation, bromine is added in intermediate M3B (6.7g, 22mmol, 1.1eq) there-necked flask Benzene (1eq.), potassium carbonate 5eq, Pd (Pph3) 4 (2%), toluene 1000ml+ ethanol 500ml+300ml water, open stirring, heating To backflow, 8h is reacted.Organic phase silica gel column chromatography, concentration, yellow powder M4B is obtained with re crystallization from toluene
Under nitrogen protection, (25mmol) 2- bromonaphthalenes are dissolved in tetrahydrofuran, and ice ethanol bath is down to -78 DEG C, and n-BuLi is added dropwise Solution, cryogenic conditions are kept, is added dropwise, temperature control 30min, intermediate M4B (4.8g, 10mmol) is dissolved in tetrahydrofuran, dripped Add in reaction bulb, be added dropwise, heat up naturally, react 8h.Watery hydrochloric acid is added in reaction solution, is extracted with ethyl acetate, it is organic Mutually concentrate, solid separates out, and is filtrated to get intermediate M5 (4.8g, 93.1%).
Intermediate M5 (5.1g, 10mmol), add in reaction bulb, add 100ml glacial acetic acid, add KI (20mmol), hypophosphorous acid hydrogen sodium (20mmol) is added, is heated to flowing back, react 5h.Filtering, with water, ethanol rinse, collection obtains Yellow powder A4 (5.3g, 79.1%).
1H NMR (400MHz, Chloroform) δ 9.11 (s, 1H), 8.84 (s, 1H), 8.31 (d, J=10.0Hz, 3H), 8.04 (dd, J=10.0,6.0Hz, 4H), 7.96-7.96 (m, 2H), 7.85 (d, J=8.0Hz, 2H), 7.63 (s, 1H), 7.57 (d, J=10.0Hz, 3H), 7.49 (s, 1H), 7.38 (s, 1H)
The synthesis of the compound A-45 of synthetic example 5.
For synthesis step with compound A4, difference is the 2- bromine dibenzofurans that bromobenzene is replaced with to equivalent, reaction knot Shu Hou, isolated white solid 5.2g.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.56(s,2H),8.35(s,1H),8.28(s, 2H), 7.79 (t, J=8.0Hz, 4H), 7.65 (s, 2H), 7.63-7.47 (m, 4H), 7.41 (s, 1H), 7.28 (s, 1H)
The compound A6 of synthetic example 6. synthesis
Synthesis step is with compound A4, after difference is that the 2- bromine triphenylenes that bromobenzene is replaced with to equivalent, reaction terminate, Isolated 5.1g.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.56(s,2H),8.35(s,1H),
8.28 (s, 2H), 8.08 (d, J=12.0Hz, 2H), 7.99 (s, 1H), 7.79 (t, J=8.0Hz, 4H), 15 7.63 (s, 1H), 7.60-7.47 (m, 6H), 7.33 (d, J=10.0Hz, 3H), 7.24 (s, 2H)
The compound A7 of synthetic example 7. synthesis
Synthesis step is with compound A1, after difference is that the 4- bromo biphenyls that 2- bromonaphthalenes are replaced with to equivalent, reaction terminate, Isolated 5.6g.
1H NMR(400MHz,Chloroform)δ8.97(s,2H),8.56(s,3H),8.35(s,1H),
20 7.88 (d, J=10.0Hz, 2H), 7.63 (d, J=12.0Hz, 4H), 7.60-7.44 (m, 6H), 7.39 (d, J =12.0Hz, 4H), 7.27 (d, J=12.0Hz, 2H)
The synthesis of the compound A-28 of synthetic example 8.
Synthesis step is bromo- (2- phenyl) the pyridine boron of the 5- that 2- bromonaphthalenes are replaced with to equivalent with compound A1, difference Acid, after reaction terminates, isolated white solid 5.1g.
1H NMR (400MHz, Chloroform) 8.97 (t, J=8.0Hz, 1H), 8.56 (s, 10H), 8.54 (s, 3H), 8.54-8.33 (m, 1H), 8.32 (s, 3H), 8.08 (d, J=12.0Hz, 1H), 8.33-7.86 (m, 3H), 7.83-7.74 (m, 2H), 7.67-7.52 (m, 3H), 7.52 (s, 2H), 7.52-7.34 (m, 4H), 7.27 (d, J=12.0Hz, 2H)
The compound A9 of synthetic example 9. synthesis
For synthesis step with compound A1, difference is 2- (4- phenyl)-pyridine that 2- bromonaphthalenes are replaced with to equivalent, reaction After end, isolated white solid 5.2g.
1H NMR(400MHz,Chloroform)δ9.29(s,2H),8.97(s,1H),8.35(s,1H),7.96(s, 2H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.41 (s, 2H), 7.25 (s, 2H)
The compound A10 of synthetic example 10. synthesis
For synthesis step with compound A1, difference is the bromo- benzofurans of 2- and anthracene that 2- bromo anthraquinones are replaced with to equivalent Quinone, 2- bromonaphthalenes are replaced with to the bromobenzene of equivalent, after reaction terminates, isolated white solid 4.8g.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 2H), 8.69 (d, J=8.0Hz, 4H), 8.37 (d, J= 10.0Hz, 3H), 8.07 (d, J=10.0Hz, 3H), 7.94 (s, 1H), 7.85 (s, 3H), 7.65 (s, 10 3H), 7.54 (d, J =12.0Hz, 4H), 7.41 (s, 3H)
The compound A11 of synthetic example 11. synthesis
For synthesis step with compound A1, difference is the bromo- benzothiophenes of 2- and anthracene that 2- bromo anthraquinones are replaced with to equivalent Quinone, after reaction terminates, isolated white solid 4.9g.
1H NMR(400MHz,Chloroform)δ9.57(s,2H),9.09(s,4H),8.97(s,2H),15 8.35(s, 2H), 7.65 (s, 4H), 7.54 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H)
The compound A12 of synthetic example 12. synthesis
For synthesis step with compound A1, difference is the bromo- 5- phenyl clicks of 9- that 2,6- dibromo-anthraquinones are replaced with to equivalent Azoles and naphthalenone, obtain faint yellow solid 4.7g.
1H NMR (400MHz, Chloroform) δ 9.13 (s, 2H), 8.97 (s, 3H), 8.92 (s, 1H), 8.28 (d, J= 10.0Hz, 4H), 8.07 (s, 2H), 7.65 (s, 4H), 7.63-7.44 (m, 9H), 7.40 (d, J=8.0Hz, 3H), 7.25 (s, 8H).
The compound A13 of synthetic example 13. synthesis
Synthesis step is 4- (2- naphthalenes)-bromobenzene that 2- bromonaphthalenes are replaced with to equivalent, obtained light with compound A1, difference Yellow solid 4.6g.
1H NMR(400MHz,Chloroform)δ9.68(s,4H),8.97(s,2H),8.35(s,2H),7.65(s, 4H), 7.54 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H)
The compound A14 of synthetic example 14. synthesis
Synthesis step with compound A1, difference be by 4- phenyl -2- chloropyrazines replace with 4, the 7- diphenyl of equivalent - 2- chloropyrazines, 2- bromonaphthalenes are replaced with to the 4- bromo biphenyls of equivalent, obtain faint yellow solid 6.6g.
1H NMR (400MHz, Chloroform) δ 8.41 (d, J=12.0Hz, 2H), 8.36-8.22 (m, 4H), 8.12- 7.67 (m, 6H), 7.80 (d, J=12.0Hz, 2H), 7.75 (dd, J=7.2,12.4Hz, 4H), 7.72 (d, J=10.0Hz, 2H), 7.70 (s, 1H), 7.71-7.46 (m, 6H), 7.34 (d, J=10.0Hz, 20H), 7.25 (d, J=12.4Hz, 6H), 7.14(s,1H),1.69(s,12H).
The compound A15 of synthetic example 15. synthesis
For synthesis step with compound A14, difference is the 4- benzene that 4,7- diphenyl -2- chloropyrazines are replaced with to equivalent Base -7- (2- pyridines) -2- chloropyrazines, obtain faint yellow solid 5.8g.
1H NMR (400MHz, Chloroform) δ 9.19 (s, 1H), 8.35 (dd, J=28.0,12.0Hz,
6H), 7.92 (s, 3H), 7.67 (s, 4H), 7.55 (s, 3H), 7.49 (s, 1H), 7.24 (d, J=4.0Hz, 6H)
The compound A16 of synthetic example 16. synthesis
Synthesis step is the 4- phenyl -2- that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A1, difference (4- bromophenyls) -2- pyrazines, obtain faint yellow solid 5.8g.
1H NMR (400MHz, Chloroform) δ 8.99 (s, 3H), 8.37 (s, 3H), 8.20 (s, 5H), 8.09 (t, J= 14.0Hz, 15H), 7.93 (dd, J=38.5,37.5Hz, 19H), 7.79 (s, 5H), 7.64 (d, J=8.0Hz, 14H), 7.60- 7.46(m,22H),7.45–7.09(m,15H).
The compound A17 of synthetic example 17. synthesis
Synthesis step is the 4- phenyl -2- that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A14, difference (6- bromonaphthalenes base) -2- pyrazines, obtain faint yellow solid 5.8g.
1H NMR(400MHz,Chloroform)δ9.15(s,1H),8.99(s,1H),8.51(s,1H),8.37(s, 1H), 8.37 (s, 1H), 8.49-8.01 (m, 8H), 8.49-7.88 (m, 6H), 7.80 (d, J=12.0Hz, 2H), 7.64 (d, J =8.0Hz, 4H), 7.60-7.46 (m, 5H), 7.40 (d, J=12.0Hz, 2H)
The compound A18 of synthetic example 18. synthesis
Synthesis step is the 4- phenyl -2- that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A1, difference (5- pyridine -2- bromines) -2- pyrazines, obtain faint yellow solid 5.8g.
1H NMR(400MHz,Chloroform)δ9.16(s,1H),8.88(s,1H),8.35(s,2H),8.32–8.18 (m, 4H), 8.10 (q, J=12.0Hz, 6H), 8.04-7.94 (m, 4H), 7.79 (s, 1H), 7.63 (s, 2H), 7.60-7.48 (m,10H),7.38(s,2H).
The compound A19 of synthetic example 19. synthesis
Synthesis step is the 2- bromonaphthalenes that bromobenzene is replaced with to equivalent with compound A10, difference,
After reaction terminates, isolated white solid 5.2g.
1H NMR(400MHz,Chloroform)δ9.53(s,2H),9.24(s,2H),8.70(s,3H),8.49–8.49 (m, 4H), 8.49 (s, 1H), 8.49-7.90 (m, 20H), 7.71 (s, 2H), 7.64 (d, J=8.0Hz, 9H), 7.90-7.45 (m, 30H), 7.78-7.45 (m, 20H), 7.60-7.51 (m, 9H), 7.48 (d, J=8.0Hz, 3H), 7.38 (d, J=4.0Hz, 6H),7.31(s,1H).
The compound A20 of synthetic example 20. synthesis
Synthesis step is with compound A11, after difference is that the bromobenzene that 2- bromonaphthalenes are replaced with to equivalent, reaction terminate, point From obtaining white solid 4.8g.
1H NMR(400MHz,Chloroform)δ8.54–8.42(m,4H),8.31(s,1H),8.25(s,1H),8.12 (d, J=4.0Hz, 4H), 8.06 (d, J=0.6Hz, 3H), 7.99 (d, J=8.0Hz, 3H), 7.77-7.74 (m, 4H), 7.77- 7.52(m,10H),7.89–7.15(m,20H),7.77–7.15(m,20H),7.41(s,1H),7.31(s,1H).
The compound A21 of synthetic example 21. synthesis
Synthesis step is the 2- phenyl -4- that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A12, difference Chloropyrazine, after reaction terminates, isolated white solid 4.9g.
1H NMR (400MHz, Chloroform) δ 8.61 (s, 11H), 8.49 (s, 11H), 8.39 (dd, J=7.6, 3.1Hz, 2H), 8.33 (d, J=16.0Hz, 33H), 8.40-8.04 (m, 116H), 8.03 (d, J=7.8Hz, 6H), 7.99 (s, 28H), 8.04-7.66 (m, 55H), 7.66-7.47 (m, 156H), 7.39 (d, J=8.0Hz, 33H), 7.19 (d, J=8.0Hz, 22H).
The compound A22 of synthetic example 22. synthesis
Synthesis step is 4- (4- (the 2- pyrroles that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A1, difference Piperidinyl)-phenyl) -2- chloropyrazines, obtain faint yellow solid 4.7g.
1H NMR (400MHz, Chloroform) δ 8.69 (s, 2H), 8.49 (s, 1H), 8.20 (s, 2H), 8.11 (d, J= 16.0Hz,3H),8.07–7.85(m,5H),8.39–7.53(m,25H),8.07–7.69(m,7H),8.28–7.53(m,21H), 7.63(s,2H),7.60–7.51(m,7H),7.38(s,2H),7.14(s,2H),6.90(s,1H).
The compound A23 of synthetic example 23. synthesis
Synthesis step is with compound A21, and difference is the bromobenzene that 2- bromonaphthalenes are replaced with to equivalent, by the chloro- 4- (phenyl of 2- The chloro- 4- of 2- (2- naphthyls) pyrazine that pyrazine replaces with equivalent obtains faint yellow solid 4.6g.
1H NMR (400MHz, Chloroform) δ 9.09 (s, 2H), 8.47 (d, J=12.0Hz, 4H), 8.32 (s, 1H), 8.31–8.04(m,11H),8.06(s,4H),8.06(s,4H),8.04–7.89(m,6H),7.79(s,2H),7.71(s,2H), 7.69-7.44 (m, 32H), 7.40 (d, J=4.0Hz, 6H), 7.19 (d, J=8.0Hz, 4H)
The compound A24 of synthetic example 24. synthesis
Synthesis step is the 4- xenyls -2- that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A1, difference Chloropyrazine, obtain faint yellow solid 6.6g.
1H NMR (400MHz, Chloroform) δ 8.95 (s, 1H), 8.49 (d, J=4.0Hz, 2H), 8.31 (d, J= 2.8Hz, 2H), 8.20 (s, 2H), 8.09 (t, J=14.0Hz, 3H), 7.97 (d, J=12.0Hz, 3H), 7.63 (s, 1H), 7.91–7.05(m,23H),7.60–7.51(m,5H),7.69–7.05(m,16H),7.51–7.32(m,7H),7.25(s,2H).
The compound A25 of synthetic example 25. synthesis
Synthesis step is the 7- phenyl -4- that 4- phenyl -2- chloropyrazines are replaced with to equivalent with compound A1, difference (4- phenyl-pyridins -2) -2- chloropyrazines, obtain faint yellow solid 5.8g.
1H NMR (400MHz, Chloroform) δ 9.18 (s, 2H), 8.49 (s, 2H), 8.43 (d, J=8.0Hz, 4H), 8.34-7.83 (m, 23H), 8.01 (d, J=16.7Hz, 6H), 8.01 (d, J=16.7Hz, 6H), 7.73 (d, J=16.0Hz, 7H), 7.63 (s, 4H), 7.52 (dt, J=20.0,12.0Hz, 25H), 7.39 (d, J=12.0Hz, 8H)
The compound A26 of synthetic example 26. synthesis
Synthesis step with compound A1, difference be by 4- phenyl -2- chloropyrazines replace with the 4- (1- naphthyls) of equivalent - 2- chloropyrazines, 2- bromonaphthalenes are replaced with to the bromobenzene of equivalent, obtain faint yellow solid 5.8g.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 2H), 8.49 (s, 2H), 8.26 (d, J=44.0Hz, 5H), 8.19-8.15 (m, 1H), 8.13 (s, 2H), 8.00 (s, 2H), 7.94 (s, 2H), 7.82 (dd, J=13.1,5.8Hz, 8H), 7.71(s,2H),7.65(s,10H),7.57–7.51(m,12H),7.47(s,4H),7.41(s,4H).
The compound A27 of synthetic example 27. synthesis
Synthesis step with compound A24, difference be by 4- xenyl -2- chloropyrazines replace with the 2- phenyl of equivalent - 7- (2- naphthyls) -4- chloropyrazines, obtain faint yellow solid 5.8g.
1H NMR (400MHz, Chloroform) δ 9.35 (s, 1H), 8.95 (s, 1H), 8.49 (d, J=4.0Hz, 2H), 8.38-8.23 (m, 4H), 8.20 (s, 2H), 8.08 (d, J=12.0Hz, 4H), 7.99 (s, 2H), 7.89 (s, 3H), 7.88- 7.74 (m, 3H), 7.62 (dd, J=12.0,8.0Hz, 7H), 7.57 (d, J=12.0Hz, 4H), 7.54 (dd, J=10.0, 8.0Hz, 8H), the analysis inspection of the specific preferably synthetic structural compounds disclosed in 7.43-7.32 (m, 4H) embodiment of the present invention Survey data row in table 1 below：
Device embodiments：
The structure of organic electroluminescence device of the present invention is preferably as follows the structure of the composition：
(1) anode/hole injection layer (HIL)/hole transmission layer (HTL)/luminescent layer (EML)/electron transfer layer (ETL)/ Electron injecting layer (EIL)/negative electrode；
(2) anode/hole transmission layer (HTL)/luminescent layer (EML)/hole blocking layer (HBL)/electron transfer layer (ETL)/ Electron injecting layer (EIL)/negative electrode
Above-mentioned "/" represents to be laminated in order between difference in functionality layer.
In the preferred embodiment, organic electroluminescence device has the luminous effect of lower operating voltage and Geng Gao Rate.
Substrate can use the substrate in conventional organic luminescence organic electroluminescence device, such as：Glass or plastics.Anode Material can use transparent high conductivity material, such as indium tin oxygen (ITO), indium zinc oxygen (IZO), tin ash (SnO2), oxygen Change zinc (ZnO) etc..Glass substrate is selected in the organic electroluminescence device of embodiment makes, ITO makees anode material.
Common hole-injecting material has CuPc, TNATA and PEDT：PSS etc..The organic electroluminescence device of the present invention Hole injection layer uses 2-TNATA.
Hole transmission layer can use N, N '-two (3- tolyls)-N, N '-diphenyl-[1,1- xenyls] -4,4 '-two Amine (TPD) or N, N ' the tri-arylamine group material such as-diphenyl-N, N '-two (1- naphthyls)-(1,1 '-xenyl) -4,4 '-diamines (NPB) Material.Hole mobile material selects NPB in the organic electroluminescence device that the present invention makes.
Organic electroluminescence device structure can be that single-shot photosphere can also be multi-luminescent layer structure.In the embodiment of the present invention Employ the structure of single-shot photosphere.Luminescent layer includes light emitting host material and luminescent dye, wherein luminescent dye and luminous master The mass ratio of body material is controlled by regulating and controlling both evaporation rates in device fabrication process, generally control luminescent dye with The evaporation rate ratio of light emitting host material is 1% to 8%, preferably 3% to 5%.
Conventional luminescent dye includes metal iridium complex Ir (ppy), FIrpic, and pure organic molecule, rubrene, DPP, DCJ, DCM etc..
Conventional light emitting host material is including BAlq, AND, CBP, mCP, TBPe etc..
Electron transport material common in the art has Alq3, Bphen, BCP, PBD etc., and the present invention selects Alq3 conducts Electron transport layer materials from the general formula compound of the present invention as the device of electron transport material with being contrasted.
Selected cathode material is LiF/Al in the organic electroluminescence device of the present invention makes.
The different materials concrete structure used in the present invention is seen below：
Above-mentioned electroluminescent organic material, those skilled in the art, which are based on known method, can voluntarily prepare or be purchased from Chemical market Buy.
Device embodiments 1. are sent out from the preferred structure molecule in general formula compound of the present invention as organic electroluminescence of the present invention Electron transport material in optical device
The present embodiment prepares 9 organic electroluminescence devices altogether, and its structure is, according to " hole injection layer on substrate (HIL) order of/hole transmission layer (HTL)/luminescent layer (EML)/electron transfer layer (ETL)/electron injecting layer (EIL)/negative electrode " Stacking, each layer are made up of following material：
ITO/2-TNATA(30nm)/NPB(20nm)/CBP：Ir (ppy) 3 (5%) (20nm)/electron transport material (50nm)/LiF(1nm)/Al；
When preparing the electron transfer layer of device of the present invention, material selection scheme is：A kind of preferred compounds of the invention or A kind of preferred compound of the present invention is adulterated with LiQ or two kinds of preferred compounds of the invention doping (doping ratios 10:90- 90:10)。
The present invention devises comparative example simultaneously, and device architecture scheme therein is identical with such scheme, simply electronics The organization plan that material selection Alq3 or Alq3 in transport layer adulterates with another current material PBD phases.
Organic electroluminescence device preparation process is as follows in the present embodiment：
The glass substrate that surface is coated with to transparent conductive film is cleaned by ultrasonic in cleaning fluid, in deionized water It is ultrasonically treated, in ethanol：Ultrasonic oil removing in acetone mixed solution, is baked under clean environment and removes moisture removal completely, and use is ultraviolet Lamp perform etching with ozone processing, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, 1 × 10-5~9 × 10-3Pa is evacuated to, upper Vacuum evaporation 2-TNATA on anode tunic is stated, regulation evaporation rate is 0.1nm/s, forms the hole injection layer that thickness is 30nm； The vacuum evaporation compound N PB on hole injection layer, form the hole transmission layer that thickness is 20nm, evaporation rate 0.1nm/ s；Luminescent layers of the vacuum evaporation EML as device on hole transmission layer, EML include material of main part and dye materials, utilize The method that multi-source steams altogether, regulation material of main part CBP evaporation rates are 0.1nm/s, the evaporation rates of dye materials Ir (ppy) 3 according to Doping ratio is set, and evaporation total film thickness is 20nm；
Total film thickness is deposited as described above, its evaporation rate is 0.1nm/s in material solution when preparing device electron transfer layer For 50nm；
For the LiF that vacuum evaporation thickness is 1nm on electron transfer layer (ETL) as electron injecting layer, thickness is 150nm's Negative electrode of the Al layers as device.
Driving voltage and current efficiency are determined under same brightness (10000cd/m2) to gained organic electroluminescence device, Performance is shown in Table 3.
Table 3：
From the device performance data of device embodiments 1-1~1-9 disclosed in table 3, in organic electroluminescence device In structure in the case of other materials identical, the adjustment of ETL materials in the devices, compare device comparative example 1-1 and device pair Ratio 1-2, can significantly decrease the operating voltage of device, and increase substantially the luminous efficiency of device.This with the present invention Series compound have deeper LUMO values and preferable electron mobility relevant.In addition, material of the present invention adulterates with LiQ In use, under the conditions of different doping ratios, lower device voltage is achieved compared with undoped with embodiment, while can In the case of keeping efficiency consistent, there is obvious extension in the life-span during which；It is doped using two kinds of compounds of the present invention In use, the voltage of its device also has obvious reduction compared with undoped with device, embodiment device also shows longer Life-span.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (11)

1. a kind of organic electroluminescence device, including first electrode, second electrode and positioned at the first electrode and second electrode Between one or more layers organic layer, comprise at least luminescent layer and electron transfer layer in the organic layer, it is characterised in that：It is described Electron transfer layer thickness is 5-100nm, and at least one is included in electron transfer layer as the compound shown in formula (I)：
Wherein, L is selected from chemical bond, C6~C12Arlydene or sub- condensed-nuclei aromatics group, C3~C12Inferior heteroaryl or sub- thick miscellaneous Aromatic hydrocarbon group；
Ar1、Ar2And Ar3It is respectively and independently selected from C6~C30Substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C30's Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group When, the substituted radical thereon is independently selected from halogen, cyano group, nitro, or selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~C6Alkoxy or thio alkoxy group, or selected from Si (R5)3, the R5Selected from C1~C6Alkyl；
R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C10Alkylidene, halogen, cyano group, nitro, C6~C30Substitution or do not take The aryl or condensed-nuclei aromatics group, C in generation3~C30Substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, R3With R4Between Cyclic structure can be interconnected to form；
Work as R1、R2、R3And R4When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, The substituted radical thereon is independently selected from halogen, cyano group, nitro, or selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~ C6Alkoxy or thio alkoxy group, or selected from Si (R5)3, the R5Selected from C1~C6Alkyl.
2. organic electroluminescence device according to claim 1, in the formula (I)：
Ar1、Ar2And Ar3It is respectively and independently selected from C6~C20Substituted aryl or condensed-nuclei aromatics group, C5~C20Substitution or non- Substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group When, the substituted radical thereon is independently selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, Alkoxy or thio alkoxy group；
Work as Ar1、Ar2And Ar3When being respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, the miscellaneous original Son is one or more O, S and N；
R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C5Alkylidene, halogen, cyano group, nitro, C6~C15Substitution or do not take The aryl or condensed-nuclei aromatics group, C in generation3~C15Substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
Work as R1、R2、R3And R4When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, The substituted radical thereon is independently selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, alcoxyl Base or thio alkoxy group；
Work as R1、R2、R3And R4When being respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, the hetero atom For one or more O, S and N.
3. organic electroluminescence device according to claim 1, in the formula (I)：
Ar1、Ar2And Ar3When being respectively and independently selected from aryl or fused ring aryl, selected from phenyl, xenyl, terphenyl, naphthyl, anthracene Base, phenanthryl, indenyl, fluoranthene base, Sanya phenyl, pyrenyl, base,Base or aphthacene base；By furyl, thienyl, pyrrole radicals And/or the phenyl of pyridine radicals substitution；2- xenyls, 3- xenyls, 4- xenyls, p- terphenyl -4- bases, p- terphenyl Base -3- bases, p- terphenyl -2- bases, m- terphenyl -4- bases, m- terphenyl -3- bases, m- terphenyl -2- bases, Benzene binaphthyl, 4- naphthylphenyls, 6- phenyl napthyls, 7- phenyl phenanthryl, 9,9 '-dimethyl fluorene, 9, the fluorenes of 9 '-spiral shell two, benzfluorene；
Or Ar1、Ar2And Ar3When being respectively and independently selected from heteroaryl, selected from furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophenes base, dibenzopyrrole base, carbazyl, the diazole of phenyl substitution, coffee quinoline base, coffee quinoline benzothiazolyl, benzo Dioxa cyclopentenyl, 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole and indolocarbazole；
R1、R2、R3And R4It is respectively and independently selected from：Hydrogen, methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl, cyano group, nitre Base, phenyl, naphthyl, Sanya phenyl, 9,9 dimethyl fluorenes, the fluorenyl of spiral shell two, furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophenes base, dibenzopyrrole base, carbazyl, the diazole of phenyl substitution, coffee quinoline base, coffee quinoline benzothiazolyl, benzo Dioxa cyclopentenyl, 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole, indolocarbazole.
4. according to any described organic electroluminescence device, the wherein Ar in formula (I) in claims 1 to 31、Ar2And Ar3No It is identical.
5. according to any described organic electroluminescence device in claims 1 to 3, it is characterised in that the electron transfer layer Include two kinds of compounds, at least one is to be as the compound shown in formula (I), the doping part by weight of both compounds 90:10 to 10:90.
6. according to any described organic electroluminescence device in claims 1 to 3, it is characterised in that the electron transfer layer Include two kinds of compounds, at least one is as the compound shown in formula (I), and another kind is LiQ, the doping of both compounds Part by weight is 90:10 to 10:90.
7. a kind of organic electroluminescence device, the device includes first electrode, second electrode and positioned at the first electrode and the One or more layers organic layer between two electrodes, luminescent layer and electron transfer layer is comprised at least in the organic layer, its feature exists In the electron transfer layer thickness is 10-40nm, and is selected from following concrete structure formulas comprising at least one in electron transfer layer Compound：
A kind of 8. structure of general formula compound as shown in following formula (I)：
Wherein, L is selected from chemical bond, C6~C12Arlydene or sub- condensed-nuclei aromatics group, C3~C12Inferior heteroaryl or sub- thick miscellaneous Aromatic hydrocarbon group；
Ar1、Ar2And Ar3It is respectively and independently selected from C6~C30Substituted or non-substituted aryl or condensed-nuclei aromatics group, C3~C30's Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group When, the substituted radical thereon is independently selected from halogen, cyano group, nitro, or selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~C6Alkoxy or thio alkoxy group, or selected from Si (R5)3, the R5Selected from C1~C6Alkyl；
R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C10Alkylidene, halogen, cyano group, nitro, C6~C30Substitution or do not take The aryl or condensed-nuclei aromatics group, C in generation3~C30Substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, R3With R4Between Cyclic structure can be interconnected to form；
Work as R1、R2、R3And R4When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, The substituted radical thereon is independently selected from halogen, cyano group, nitro, or selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~ C6Alkoxy or thio alkoxy group, or selected from Si (R5)3, the R5Selected from C1~C6Alkyl.
9. general formula compound according to claim 8, in the formula (I)：
Ar1、Ar2And Ar3It is respectively and independently selected from C6~C20Substituted aryl or condensed-nuclei aromatics group, C5~C20Substitution or non- Substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
Work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group When, the substituted radical thereon is independently selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, Alkoxy or thio alkoxy group；
Work as Ar1、Ar2And Ar3When being respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, the miscellaneous original Son is one or more O, S and N；
R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C5Alkylidene, halogen, cyano group, nitro, C6~C15Substitution or do not take The aryl or condensed-nuclei aromatics group, C in generation3~C15Substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group；
Work as R1、R2、R3And R4When being respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group, The substituted radical thereon is independently selected from F, cyano group, or selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3, alkenyl, alcoxyl Base or thio alkoxy group；
Work as R1、R2、R3And R4When being respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, the hetero atom For one or more O, S and N.
10. general formula compound according to claim 8, in the formula (I)：
Ar1、Ar2And Ar3When being respectively and independently selected from aryl or fused ring aryl, selected from phenyl, xenyl, terphenyl, naphthyl, anthracene Base, phenanthryl, indenyl, fluoranthene base, Sanya phenyl, pyrenyl, base,Base or aphthacene base；By furyl, thienyl, pyrrole radicals And/or the phenyl of pyridine radicals substitution；2- xenyls, 3- xenyls, 4- xenyls, p- terphenyl -4- bases, p- terphenyl Base -3- bases, p- terphenyl -2- bases, m- terphenyl -4- bases, m- terphenyl -3- bases, m- terphenyl -2- bases, Benzene binaphthyl, 4- naphthylphenyls, 6- phenyl napthyls, 7- phenyl phenanthryl, 9,9 '-dimethyl fluorene, 9, the fluorenes of 9 '-spiral shell two, benzfluorene；
Or Ar1、Ar2And Ar3When being respectively and independently selected from heteroaryl, selected from furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophenes base, dibenzopyrrole base, carbazyl, the diazole of phenyl substitution, coffee quinoline base, coffee quinoline benzothiazolyl, benzo Dioxa cyclopentenyl, 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole and indolocarbazole；
R1、R2、R3And R4It is respectively and independently selected from：Hydrogen, methyl, ethyl, isopropyl, the tert-butyl group, cyclopenta, cyclohexyl, cyano group, nitre Base, phenyl, naphthyl, Sanya phenyl, 9,9 dimethyl fluorenes, the fluorenyl of spiral shell two, furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridine radicals, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophenes base, dibenzopyrrole base, carbazyl, the diazole of phenyl substitution, coffee quinoline base, coffee quinoline benzothiazolyl, benzo Dioxa cyclopentenyl, 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole, indolocarbazole.
11. general formula compound according to claim 8, selected from following concrete structure formulas：
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