CN107833974B - A kind of novel electroluminescent device - Google Patents

A kind of novel electroluminescent device Download PDF

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CN107833974B
CN107833974B CN201710565557.3A CN201710565557A CN107833974B CN 107833974 B CN107833974 B CN 107833974B CN 201710565557 A CN201710565557 A CN 201710565557A CN 107833974 B CN107833974 B CN 107833974B
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CN107833974A (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 included at least in the organic layer, it is characterised in that：The electron-transport layer thickness be 5-100nm, and in electron transfer layer comprising at least one by formula (I) compound represented：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, 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 that 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 novel 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, regards Angular width, light-weight, composition and a series of advantage such as simple for process, 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, manufacturing cost is but less than response speed The liquid crystal display of same resolution ratio, therefore, organic electroluminescence device has broad application prospects.
As OLED technology is in the continuous propulsion for illuminating and showing two big fields, people are for influencing OLED device 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 device structure, the organic of following type 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 the electron mobility of Alq3 is relatively low (about in 10-6cm2/Vs).In order to improve the electronic transmission performance of electroluminescence device, researcher has done a large amount 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 Electron-transport 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) it is used as electron-transport With injection layer material (with Ba/Al and individually use Al as cathode compared with), the electron injection and biography of device are significantly improved It is defeated, improve electroluminescence efficiency.Kodak is in United States Patent (USP) (publication number US 2006/0204784 and US 2007/ 0048545) in, mixed electronic transport layer is mentioned, using the electricity of a kind of material of low lumo energy and another low bright voltage Sub- transmission material and other materials such as metal material etc. are adulterated.
Ideal electron transport material, it should the characteristic with following several respects：With reversible electrochemical reducting reaction； HOMO and lumo energy are suitable；Electron mobility is high；Good film-forming property；Tg high；It is preferably able to blocking hole.From compound structure Aspect, it is desirable that molecule contains electron deficient structural unit, receives electronic capability with good；Molecular weight is sufficiently large, ensures have Higher Tg, to have good thermal stability, while molecular weight cannot be too big, so that vacuum evaporation forms a film.
The electron transport material performance being currently known is unsatisfactory, and industry is still badly in need of developing new electron transport material.
Invention content
That the technical problem to be solved in the present invention is to provide a kind of operating voltages is low, luminous efficiency is high, the Organic Electricity of long lifespan Electroluminescence device.Such novel electroluminescent device has selected a kind of novel electron transport material.
Another technical problems to be solved of the invention are to provide a kind of novel general formula compound of good performance.
To solve the above problems, the present 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 included at least in the organic layer And electron transfer layer, the electron-transport layer thickness be 5-100nm, and in electron transfer layer comprising at least one by formula (I) Compound represented：
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 Ar1、Ar2And Ar3On substituent group independently select From halogen, cyano, nitro, or it is selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~C6Alkoxy or thio alkoxy base Group, or it is selected 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, 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 Ar1、Ar2And Ar3On substituent group be independently selected from halogen, cyano, nitro, or be selected from C1~C10Alkyl or cycloalkyl, Alkenyl, C1~C6Alkoxy or thio alkoxy group, or be 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 monocycle or polycyclic, aromatic monocycle or condensed ring can include hetero atom 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 other than carbon atom at atom, these rings there can be substituent group, and the carbon atom for constituting ring can also Form ketone group.As the example of these rings, pentamethylene ring, cyclohexane ring, dicyclopentenyl ring, nafoxidine ring, tetrahydrochysene can be enumerated The ester ring etc. that carbon atom in furan nucleus, piperidine ring and pentamethylene ring and cyclohexane ring is replaced by ketone group.As fragrance The monocycle or condensed ring of race, the preferably monocycle of C6~C30 or condensed ring, can enumerate phenyl ring, naphthalene nucleus etc. as an example；As comprising miscellaneous The monocycle of atom is polycyclic, preferably pyrrole ring, benzopyrrole ring, pyridine ring, indole ring, N- phenyl substituted indoles ring, thiophene Pheno ring, benzothiophene ring, furan nucleus, benzofuran ring etc..
Specifically, as the above-mentioned Ar of definition1、Ar2And Ar3With R1、R2、R3And R4Refer to being selected from when being respectively and independently selected from aryl Aromatics ring system with certain amount ring skeleton carbon atom, including single ring architecture substituent group is such as phenyl, also includes covalent The aromatic ring substituents of connection structure are rolled into a ball such as xenyl, terphenyl.
Further, in organic electroluminescence device of the invention, it is used as in the logical formula (I) of 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 When group, the Ar1、Ar2And Ar3On substituent group be independently selected from and preferably be selected from F, cyano, or be selected from C1~C5Alkyl or cycloalkanes Base, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl When group, the hetero atom on the heteroaryl or condensed hetero ring aromatic hydrocarbon group is preferably one or more O, S and N.
Further, in organic electroluminescence device of the invention, it is used as in the logical formula (I) of 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, it is used as in the logical formula (I) of electron transport layer materials, Ar1、Ar2And Ar3Independently preferred aryl or fused ring aryl group include：Phenyl, xenyl, terphenyl, naphthalene, anthracene Base, phenanthryl, indenyl, fluoranthene base, triphenylene, pyrenyl, base,Base or aphthacene base；By furyl, thienyl, pyrrole radicals And/or the phenyl of pyridyl group 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 naphthalene is made of 1- naphthalenes and 2- naphthalenes；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 of 1- fluorenyls, 2- fluorenyls, 3- fluorenyls, 4- fluorenyls and 9- fluorenyls In；The fluorenyl derivative is selected from the group being made of 9,9 '-dimethyl fluorenes, 9,9 '-spiral shell, two fluorenes and benzfluorene；The pyrene Base is in the group being made of 1- pyrenyls, 2- pyrenyls and 4- pyrenyls；The aphthacene base is selected from by 1- aphthacenes base, 2- and four In the group that phenyl and 9- aphthacene bases are formed.
Further, in formula (I), Ar1、Ar2And Ar3Independently preferred heteroaryl groups include：Furyl, phenyl Furyl, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indeno Fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, Benzoquinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, phenyl substitution two At least one of azoles, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group, wherein the carbazyl derives Object 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, it is used as in the logical formula (I) of electron transport layer materials, R1、 R2、R3And R4Independently it preferably is selected from hydrogen, C1~C5Alkylidene, halogen, cyano, 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 When group, the R1、R2、R3And R4On substituent group be independently selected from and preferably be selected from F, cyano, or be selected from C1~C5Alkyl or cycloalkanes Base, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, work as R1、R2、R3And R4It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl When group, the hetero atom on the heteroaryl or condensed hetero ring aromatic hydrocarbon group 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, Tertiary butyl, cyclopenta, cyclohexyl, cyano, nitro, benzene (I) base, naphthalene, triphenylene, 9,9 dimethyl fluorenes, two fluorenyl of spiral shell, furan Mutter base, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, Fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran Base, indyl, benzoquinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, benzene At least one of diazole, coffee quinoline base, coffee quinoline benzothiazolyl and the benzodioxole group of base substitution, wherein 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, the thickness of organic electroluminescence device of the invention, the preferably described luminescent layer is 5nm to 50nm, more The thickness of preferred luminescent layer is 10nm to 30nm.It is preferred that its electron-transport layer thickness is 5-100nm, more preferably electron-transport Layer thickness is 10-40nm.
Further, may include two kinds of compounds in electron transfer layer in organic electroluminescence device of the invention, One kind is, by formula (I) compound represented, another electron transport material being preferably LiQ, the doping weight of both compounds Ratio is 90:10 to 10:90.
Further, the preferred example as the organic electroluminescence device of the present invention, can enumerate and select following representatives Organic electroluminescence devices of the property compound A1~A27 as electron transport layer materials.
The present invention organic electroluminescence device have excellent photoelectricity performance, have relatively low device rise it is bright and Operating voltage, while there is relatively high device efficiency, and device lasts a long time.
Present invention simultaneously provides a kind of novel quinazoline substitution anthracene derivants to have structure shown in logical formula (I) as follows：
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 Ar1、Ar2And Ar3On substituent group independently select From halogen, cyano, nitro, or it is selected from C1~C10Alkyl or cycloalkyl, alkenyl, C1~C6Alkoxy or thio alkoxy base Group, or it is selected 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, 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 R4It is respectively and independently selected from substituted aryl, condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group When, the Ar1、Ar2And Ar3On substituent group be independently selected from halogen, cyano, nitro, or be selected from C1~C30Alkyl or cycloalkanes Base, alkenyl, C1~C6Alkoxy or thio alkoxy group, or be 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 monocycle or condensed ring, can includes hetero atom in these rings, wherein as aliphatic The example of monocycle, for example, R3With R4Two groups of middle arbitrary neighborhood connect to form aliphatic five-membered ring, hexatomic ring, these rings Constituting atom can also be hetero atom other than carbon atom, these rings can have substituent group, constitute 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, The ester ring etc. that carbon atom in tetrahydrofuran ring, piperidine ring and pentamethylene ring and cyclohexane ring is replaced by ketone group.As Aromatic monocycle or condensed ring, the preferably monocycle of C6~C30 or condensed ring, can enumerate phenyl ring, naphthalene nucleus etc. as an example；As packet Containing heteroatomic monocycle 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 R4Refer to being selected from when being respectively and independently selected from aryl Aromatics ring system with certain amount ring skeleton carbon atom, including single ring architecture substituent group is such as phenyl, also includes covalent The aromatic ring substituents of connection 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 substituent group is also wrapped such as naphthalene, anthryl Include building stone such as benzene binaphthyl, naphthalene xenyl, the biphenyl connection that condensed cyclic structure substituent group is connected with single ring architecture aryl Anthryl etc. further includes being covalently attached the thick aromatic ring substituents group of structure 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 It includes that one or more is selected from B, N, O, S, P (=O), the hetero atom of Si and P and the list with ring carbon atom to refer to when 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 When group, the Ar1、Ar2And Ar3On substituent group be independently selected from and preferably be selected from F, cyano, or be selected from C1~C5Alkyl or cycloalkanes Base, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, work as Ar1、Ar2And Ar3It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl When group, the hetero atom on the heteroaryl or condensed hetero ring aromatic hydrocarbon group 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 preferred aryl or fused ring aryl group include：Benzene Base, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, indenyl, fluoranthene base, triphenylene, pyrenyl, base,Base or aphthacene Base；The phenyl replaced by furyl, thienyl, pyrrole radicals and/or pyridyl group；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 naphthalene is made of 1- naphthalenes and 2- naphthalenes；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 of 1- fluorenyls, 2- fluorenyls, 3- fluorenyls, 4- fluorenyls and 9- fluorenyls In；The fluorenyl derivative is selected from the group being made of 9,9 '-dimethyl fluorenes, 9,9 '-spiral shell, two fluorenes and benzfluorene；The pyrenyl In the group being made 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 preferred heteroaryl groups include：Furyl, phenyl Furyl, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indeno Fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, Benzoquinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, phenyl substitution two At least one of azoles, coffee quinoline base, coffee quinoline benzothiazolyl and benzodioxole group, wherein the carbazyl derives Object can include but is not limited in 9- phenyl carbazoles, 9- naphthyl carbazoles benzo carbazole, dibenzo-carbazole and indolocarbazole It is at least one.
Further, in formula (I), R1、R2、R3And R4Independently it preferably is selected from hydrogen, C1~C5Alkylidene, halogen, cyano, 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 When group, the R1、R2、R3And R4On substituent group be independently selected from and preferably be selected from F, cyano, or be selected from C1~C5Alkyl or cycloalkanes Base, Si (CH3)3, alkenyl, alkoxy or thio alkoxy group.
Further, work as R1、R2、R3And R4It is respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aryl When group, the hetero atom on the heteroaryl or condensed hetero ring aromatic hydrocarbon group 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, Tertiary butyl, cyclopenta, cyclohexyl, cyano, nitro, benzene (I) base, naphthalene, triphenylene, 9,9 dimethyl fluorenes, two fluorenyl of spiral shell, furan Mutter base, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, Fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran Base, indyl, benzoquinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, benzene At least one of diazole, coffee quinoline base, coffee quinoline benzothiazolyl and the benzodioxole group of base substitution, wherein 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 1000 hereinafter, more preferably 450~900, Further preferably 600~800, molecular size range suitable so is all brought just to the synthesis of compound, dissolving, vapor deposition Profit, 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 It is only representative to close object.
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 Service life has very important practical significance in the manufacture of organic electroluminescence device.
The advantages of the compounds of this invention, is：
1, the compounds of this invention structure design selects single quinazoline substitution anthracene structure as parent nucleus group, and design can in this way Protect parent nucleus active site, to keep compound stability have 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, are conducive to the stability of material；
2, there is the precursor structure of the compounds of this invention coplanarity well, derivative to be passed with higher carrier Defeated property, so as to significantly reduce the operating voltage of the device using such material, while the high migration that compound has Rate also makes the thickness control of material have broader adjusting range, increases the film thickness of material and can not significantly affect the work of device Make voltage；
3, 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 conducive to the film forming of molecule；The change for replacing 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 increase The luminous efficiency of device.
Description of the drawings
From the detailed description below in conjunction with the accompanying drawings to the embodiment of the present invention, these and/or other aspects of the invention and Advantage will become clearer and be easier to understand, wherein：
Fig. 1 is the highest occupied molecular orbital (HOMO) of the compounds of this invention A1.
Fig. 2 is the lowest unoccupied molecular orbital (LUMO) of the compounds of this invention A1.
Fig. 3 is the highest occupied molecular orbital HOMO of the compounds of this invention A5.
Fig. 4 is the lowest unoccupied molecular orbital LUMO of the compounds of this invention A5.
Specific implementation mode
Below with reference to following examples set forth the preparation methods of the representation compound of the present invention.Due to the compounds of this invention Skeleton having the same, those skilled in the art be based on these preparation methods, can by known functional group's conversion method, readily Synthesize other the compound of the present invention.Hereinafter, also providing the preparation method and photism of the luminescent device comprising the compound Matter measures.
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.
Various chemicals used in synthetic example for example petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, Bis- (bromomethyl) benzene of dichloromethane, carbon tetrachloride, acetone, 1,2-, 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- naphthalenes) -6- The bases such as phenyl carbazole, N- phenyl carbazole -3- boric acid, 9- (2- naphthalenes) carbazole -3- boric acid, bis- bromo- 2,5- diaminobenzenes of 1,4- Industrial chemicals chemical products can be commercially available at home.The compound for the synthetic method that 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 (4000 QTRAP) and cloth Luke Nuclear Magnetic Resonance (400M).
The synthesis of 1. compound A1 of synthetic example
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 overnight, reaction solution column chromatography concentrates, petroleum ether for reaction It boils and washes, 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+ ethyl alcohol 500ml+300ml water are opened 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 keeps cryogenic conditions, is added dropwise, temperature control 30min, intermediate M3 (4.8g, 10mmol) is dissolved in tetrahydrofuran, is added dropwise Enter in reaction bulb, be added dropwise, heat up naturally, reacts 8h.Dilute hydrochloric acid is added in reaction solution, is extracted with ethyl acetate, organic phase Concentration, solid are precipitated, and intermediate M4 (4.8g, 93.1%) is obtained by filtration.
Intermediate M4 (5.1g, 10mmol) is added in reaction bulb, and 100ml glacial acetic acid is added, and potassium iodide is added (20mmol) is added hypophosphorous acid hydrogen sodium (20mmol), is heated to flowing back, react 5h.Filtering, with water, ethanol rinse, collection obtains Yellow powder A1 (5.3g, 79.1%).
The magnetic resonance spectroscopy data of compound A1：
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 synthesis of 2. compound A2 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 4- (2- naphthalenes) of equivalent with compound A1, difference Pyrazine,
After reaction, isolated white solid 6.2g.
The magnetic resonance spectroscopy data of compound A2：
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 3. compound A-13 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 2- phenyl -4- chlorine of equivalent with compound A1, difference Pyrazine,
After reaction, 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 synthesis of 4. compound A4 of synthetic example
Synthesis step is to replace with 2- bromo anthraquinones into 2, the 6- dibromo-anthraquinones of equivalent, obtain with compound A1, difference 4.6 g of intermediate M2B.
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+ ethyl alcohol 500ml+300ml water are opened 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+ ethyl alcohol 500ml+300ml water open stirring, heating To reflux, 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 keeps cryogenic conditions, is added dropwise, temperature control 30min, intermediate M4B (4.8g, 10mmol) is dissolved in tetrahydrofuran, drips It is added in reaction bulb, is added dropwise, heat up naturally, react 8h.Dilute hydrochloric acid is added in reaction solution, is extracted with ethyl acetate, it is organic It mutually concentrates, solid is precipitated, and intermediate M5 (4.8g, 93.1%) is obtained by filtration.
Intermediate M5 (5.1g, 10mmol) is added in reaction bulb, and 100ml glacial acetic acid is added, and potassium iodide is added (20mmol) is added hypophosphorous acid hydrogen sodium (20mmol), 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 5. compound A-45 of synthetic example
Synthesis step is to replace with bromobenzene into the 2- bromine dibenzofurans of equivalent, reacts and tie with compound A4, difference 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), (s, 1H) of 7.79 (t, J=8.0Hz, 4H), 7.65 (s, 2H), 7.63-7.47 (m, 4H), 7.41 (s, 1H), 7.28
The synthesis of 6. compound A6 of synthetic example
With compound A4, difference is to replace with bromobenzene into the 2- bromine triphenylenes of equivalent synthesis step, after reaction,
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 synthesis of 7. compound A7 of synthetic example
With compound A1, difference is to replace with 2- bromonaphthalenes into the 4- bromo biphenyls of equivalent synthesis step, after reaction, 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 8. compound A-28 of synthetic example
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, 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 synthesis of 9. compound A9 of synthetic example
With compound A1, difference is to replace with 2- bromonaphthalenes into 2- (4- phenyl)-pyridine of equivalent synthesis step,
After reaction, 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 synthesis of 10. compound A10 of synthetic example
With compound A1, difference is to replace with 2- bromo anthraquinones into the bromo- benzofurans of 2- of equivalent and anthracene synthesis step 2- bromonaphthalenes are replaced with the bromobenzene of equivalent by quinone, after reaction, 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 synthesis of 11. compound A11 of synthetic example
With compound A1, difference is to replace with 2- bromo anthraquinones into the bromo- benzothiophenes of 2- of equivalent and anthracene synthesis step Quinone, after reaction, 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 synthesis of 12. compound A12 of synthetic example
With compound A1, difference is to replace with 2,6- dibromo-anthraquinones into the 9- bromo- 5- phenyl clicks of equivalent synthesis step 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 synthesis of 13. compound A13 of synthetic example
Synthesis step is to replace with 2- bromonaphthalenes into 4- (2- naphthalenes)-bromobenzene of equivalent, obtain 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), (s, 8H) of 7.54 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.25
The synthesis of 14. compound A14 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into 4, the 7- diphenyl-of equivalent with compound A1, difference 2- bromonaphthalenes are replaced with the 4- bromo biphenyls of equivalent, obtain faint yellow solid 6.6g by 2- chloropyrazines.
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 synthesis of 15. compound A15 of synthetic example
With compound A14, difference is to replace with 4,7- diphenyl -2- chloropyrazines into the 4- benzene of equivalent synthesis step 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 synthesis of 16. compound A16 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 4- phenyl -2- of 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 synthesis of 17. compound A17 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 4- phenyl -2- of 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 synthesis of 18. compound A18 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 4- phenyl -2- of 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 synthesis of 19. compound A19 of synthetic example
With compound A10, difference is to replace with bromobenzene into the 2- bromonaphthalenes of equivalent synthesis step,
After reaction, 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 synthesis of 20. compound A20 of synthetic example
Synthesis step is to replace with 2- bromonaphthalenes into the bromobenzene of equivalent, after reaction, divide with compound A11, difference 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 synthesis of 21. compound A21 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 2- phenyl -4- of equivalent with compound A12, difference Chloropyrazine, after reaction, 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 synthesis of 22. compound A22 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into 4- (4- (the 2- pyrroles of 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 synthesis of 23. compound A23 of synthetic example
Synthesis step is with compound A21, and difference is to replace with 2- bromonaphthalenes into the bromobenzene of equivalent, by the chloro- 4- (phenyl of 2- The chloro- 4- of 2- (2- naphthalenes) 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 synthesis of 24. compound A24 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 4- xenyls -2- of equivalent with compound A1, difference Chloropyrazine obtains 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 synthesis of 25. compound A25 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 7- phenyl -4- of 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 synthesis of 26. compound A26 of synthetic example
Synthesis step is to replace with 4- phenyl -2- chloropyrazines into the 4- (1- naphthalenes)-of equivalent with compound A1, difference 2- bromonaphthalenes are replaced with the bromobenzene of equivalent by 2- chloropyrazines, 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 synthesis of 27. compound A27 of synthetic example
Synthesis step is to replace with 4- xenyl -2- chloropyrazines into the 2- phenyl-of equivalent with compound A24, difference 7- (2- naphthalenes) -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 specific preferably synthetic structural compounds disclosed in 7.43-7.32 (m, 4H) embodiment of the present invention Measured data arranges in table 1 below：
Device embodiments：
The structure of organic electroluminescence device of the present invention is preferably as described below the structure of composition：
(1) anode/hole injection layer (HIL)/hole transmission layer (HTL)/luminescent layer (EML)/electron transfer layer (ETL)/ Electron injecting layer (EIL)/cathode；
(2) anode/hole transmission layer (HTL)/luminescent layer (EML)/hole blocking layer (HBL)/electron transfer layer (ETL)/ Electron injecting layer (EIL)/cathode；
Above-mentioned "/" indicates to be laminated in order between different function layer.
In the preferred embodiment, organic electroluminescence device has lower operating voltage and higher luminous effect Rate.
Substrate can use the substrate in conventional organic luminescence organic electroluminescence device, such as：Glass or plastics.Anode Transparent high conductivity material, such as indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), oxygen may be used in material Change zinc (ZnO) etc..Glass substrate, ITO is selected to make anode material in the organic electroluminescence device of embodiment makes.
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.
N, N '-two (3- tolyls)-N, N '-diphenyl-[1,1- xenyls] -4,4 '-two may be used in hole transmission layer The tri-arylamine groups such as amine (TPD) or N, N '-diphenyl-N, N '-two (1- naphthalenes)-(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 Use the structure of single-shot photosphere.Luminescent layer includes light emitting host material and luminescent dye, wherein luminescent dye and the master that shines The mass ratio of body material is controlled by the evaporation rate both regulated and controled in device fabrication process, usually control luminescent dye with The evaporation rate ratio of light emitting host material is 1% to 8%, preferably 3% to 5%.
Common luminescent dye include metal iridium complex Ir (ppy), FIrpic and pure organic molecule, rubrene, DPP, DCJ, DCM etc..
Common light emitting host material includes BAlq, AND, CBP, mCP, TBPe etc..
Electron transport material common in the art has Alq3, Bphen, BCP, PBD etc., the present invention to select Alq3 conducts Electron transport layer materials are compared with the general formula compound of the present invention is selected as the device of electron transport material.
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 It buys.
Device embodiments 1. select the preferred structure molecule in general formula compound of the present invention to be sent out as organic electroluminescence of the present invention Electron transport material in optical device
The present embodiment prepares 9 organic electroluminescence devices altogether, and structure is, according to " hole injection layer on substrate (HIL)/hole transmission layer (HTL)/luminescent layer (EML)/electron transfer layer (ETL)/electron injecting layer (EIL)/cathode " it is suitable Sequence is laminated, and each layer is made 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 adulterate (doping ratios 10:90- 90:10)。
The present invention devises comparative example simultaneously, and device architecture scheme therein is identical as said program, only electronics The organization plan that material selection Alq3 or Alq3 in transport layer is adulterated 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 solution, in deionized water It is ultrasonically treated, in ethyl alcohol：Ultrasonic oil removing, is baked under clean environment and completely removes moisture, use is ultraviolet in acetone mixed solution Lamp performs etching and ozone treatment, and low energy cation beam bombarded surface is used in combination；
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, adjusting 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 forms 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, are utilized The method that multi-source steams altogether, adjusting material of main part CBP evaporation rates be 0.1nm/s, 3 evaporation rates of dye materials Ir (ppy) according to Doping ratio is set, and vapor deposition 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 The Al layers of cathode as device.
Driving voltage and current efficiency are measured under same brightness (10000cd/m2) to gained organic electroluminescence device, Performance is shown in Table 3.
Table 3：
The device performance data of device embodiments 1-1~1-9 disclosed in table 3 are as it can be seen that in organic electroluminescence device In the case of other materials is identical in structure, 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 in the present invention Series compound have deeper LUMO values and preferable electron mobility it is related.In addition, material of the present invention is adulterated with LiQ In use, under the conditions of different doping ratios, lower device voltage is achieved compared with undoped with embodiment, while can It keeps under efficiency unanimous circumstances, there is apparent extension in the service life during which；Two kinds of compounds using the present invention are doped In use, the voltage of its device also has apparent reduction, embodiment device also to show longer compared with undoped device Service life.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, 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 also be regarded as the disclosure of the present invention.

Claims (9)

1. a kind of organic electroluminescence device, including first electrode, second electrode and it is located at the first electrode and second electrode Between multilayer organic layer, luminescent layer and electron transfer layer are included at least in the organic layer, it is characterised in that：The electronics passes Defeated layer thickness be 5-100nm, and in electron transfer layer comprising at least one by formula (I) compound represented：
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 Ar1、Ar2And Ar3On substituent group be independently selected from halogen, cyano, nitro, or be selected from C1~C10Alkyl or cycloalkanes Base, alkenyl, C1~C6Alkoxy or thio alkoxy group, or be 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, 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 Ar1、Ar2And Ar3On substituent group be independently selected from halogen, cyano, nitro, or be selected from C1~C10Alkyl or cycloalkyl, Alkenyl, C1~C6Alkoxy or thio alkoxy group, or be selected from Si (R5)3, the R5Selected from C1~C6Alkyl；
Ar wherein in formula (I)1、Ar2And Ar3It differs.
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 Ar1、Ar2And Ar3On substituent group be independently selected from F, cyano, or be 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 heteroaryl Hetero atom on base or condensed hetero ring aromatic hydrocarbon group is one or more O, S and N；
R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C5Alkylidene, halogen, cyano, 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 R1、R2、R3And R4On substituent group be independently selected from F, cyano, or be selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3、 Alkenyl, alkoxy 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 heteroaryl Or the hetero atom on condensed hetero ring aromatic hydrocarbon group is 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, naphthalene, anthracene Base, phenanthryl, indenyl, fluoranthene base, triphenylene, pyrenyl, base,Base or aphthacene base；By furyl, thienyl, pyrrole radicals And/or the phenyl of pyridyl group 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 fluorenes, 9,9 '-spiral shell, two fluorenes, benzfluorene；
Or Ar1、Ar2And Ar3When being respectively and independently selected from heteroaryl, selected from furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophene, 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, tertiary butyl, cyclopenta, cyclohexyl, cyano, nitre Base, phenyl, naphthalene, triphenylene, 9,9 dimethyl fluorenes, two fluorenyl of spiral shell, furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophene, 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 organic electroluminescence device in claims 1 to 3, which is characterized in that the electron transfer layer Include two kinds of compounds, at least one is, by formula (I) compound represented, the doping weight ratio of both compounds is 90:10 to 10:90.
5. according to any organic electroluminescence device in claims 1 to 3, which is characterized in that the electron transfer layer Include two kinds of compounds, at least one is, by formula (I) compound represented, another kind is LiQ, the doping of both compounds Weight ratio is 90:10 to 10:90.
6. a kind of organic electroluminescence device, which includes first electrode, second electrode and positioned at the first electrode and the Multilayer organic layer between two electrodes includes at least luminescent layer and electron transfer layer in the organic layer, which is characterized in that described Electron-transport layer thickness is 10-40nm, and includes at least one chemical combination selected from following concrete structure formulas in electron transfer layer Object：
7. a kind of general formula compound, the structure 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~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 Ar1、Ar2And Ar3On substituent group be independently selected from F, cyano, or be selected from C1~C5Alkyl or cycloalkyl, alkenyl, Alkoxy, thio alkoxy group, or it is selected from Si (CH3)3；
Work as Ar1、Ar2And Ar3When being respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, the heteroaryl Hetero atom on base or condensed hetero ring aromatic hydrocarbon group is one or more O, S and N；
R1、R2、R3And R4It is respectively and independently selected from hydrogen, C1~C5Alkylidene, halogen, cyano, 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 R1、R2、R3And R4On substituent group be independently selected from F, cyano, or be selected from C1~C5Alkyl or cycloalkyl, Si (CH3)3、 Alkenyl, alkoxy 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 heteroaryl Or the hetero atom on condensed hetero ring aromatic hydrocarbon group is one or more O, S and N.
8. general formula compound according to claim 7, in the formula (I)：
Ar1、Ar2And Ar3When being respectively and independently selected from aryl or fused ring aryl, selected from phenyl, xenyl, terphenyl, naphthalene, anthracene Base, phenanthryl, indenyl, fluoranthene base, triphenylene, pyrenyl, base,Base or aphthacene base；By furyl, thienyl, pyrrole radicals And/or the phenyl of pyridyl group 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 fluorenes, 9,9 '-spiral shell, two fluorenes, benzfluorene；
Or Ar1、Ar2And Ar3When being respectively and independently selected from heteroaryl, selected from furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophene, 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, tertiary butyl, cyclopenta, cyclohexyl, cyano, nitre Base, phenyl, naphthalene, triphenylene, 9,9 dimethyl fluorenes, two fluorenyl of spiral shell, furyl, benzofurane base, thienyl, tolylthiophene Base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, pyrazinyl, fluorenyl, indeno fluorenyl, quinoline, triazine radical, benzo Furyl, benzothienyl, phentriazine, benzopyrazines, isobenzofuran-base, indyl, benzoquinoline, dibenzofurans Between base, dibenzothiophene, 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.
9. general formula compound according to claim 7 is selected from following concrete structure formulas：
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