CN107827853A - Blue light-emitting compound, organic electroluminescence device and its application - Google Patents

Blue light-emitting compound, organic electroluminescence device and its application Download PDF

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CN107827853A
CN107827853A CN201711141664.XA CN201711141664A CN107827853A CN 107827853 A CN107827853 A CN 107827853A CN 201711141664 A CN201711141664 A CN 201711141664A CN 107827853 A CN107827853 A CN 107827853A
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phenanthryl
anthryl
naphthyl
blue light
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CN107827853B (en
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不公告发明人
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Nanjing Topto Materials Co Ltd
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Abstract

The present invention relates to field of light emitting materials, specifically, there is provided a kind of blue light-emitting compound, organic electroluminescence device and its application.The structural formula of the blue light-emitting compound is as follows：Wherein, R1For any one in hydrogen, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical；R2For any one in hydrogen, C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical；R3For any one in hydrogen, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical；R4For any one in hydrogen, C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical.The compound is used to that in luminescent device luminous efficiency and device lifetime can be improved.

Description

Blue light-emitting compound, organic electroluminescence device and its application
Technical field
The present invention relates to field of light emitting materials, in particular to a kind of blue light-emitting compound, organic electroluminescence Part and its application.
Background technology
Organic electroluminescence device (Organic Light-emitting Devices) is to utilize the spontaneous of following principle Property luminescent device：When a field is applied, fluorescent material recombining by positive pole injected holes and negative pole injected electrons And light.
Since the layered-type organic electroluminescence device of low voltage drive is by Eastman Kodak Company's Since C.W.Tang reports (Applied Physics Letters, Volume page 51,913,1987), people are to will be organic The organic electroluminescence device that material is used as constituent material has carried out many researchs.Tang et al. uses three (8-hydroxyquinoline) aluminium Hole transmission layer is used as luminescent layer, and by the use of triphenyl diamine derivative.The advantages of layer structure is can to improve hole note Enter the efficiency of luminescent layer, and the effect of the excited particles formed by blocking and recombinating negative pole injected electrons can be improved Rate, the excited particles formed in luminescent layer can also be closed.As the structure of organic electroluminescence device, there is hole transport The double-layer structure of (injection) layer and electric transmission and luminescent layer, and passed with hole transport (injection) layer, luminescent layer and electronics The three-decker of defeated (injection) layer is known.In order to improve the recombination efficiency of injected holes and electronics in layered-type device, People studied by the structure to device and the method for formation device.
Known chelate, such as three (8-hydroxyquinoline) aluminium, coumarin derivative, tetraphenylbutadiene derivative, double benzene Vinyl arylene derivative and oxadiazole derivatives can be used as luminescent material.It is reported that these luminescent materials can be sent The blue light of visibility region is expected that by obtaining chromatic display using these luminescent materials to feux rouges.But it can send out Go out the organic electroluminescence device of the blue light with high color purity and high-luminous-efficiency, be always the target that the field is pursued.This Also it is related to for chemists and develops the functionalization materials of various structures and provide great opportunities and challenges.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of blue light-emitting compound, and the blue light-emitting compound can be used as blueness Fluorescent host material, for driving voltage can be reduced in organic electroluminescence device, improve luminous efficiency, brightness, thermostabilization Property, color purity and device lifetime.
The second object of the present invention in providing a kind of application of above-mentioned blue light-emitting compound in luminescent device is prepared, Above-mentioned blue light-emitting compound is applied in luminescent device, it is possible to increase the luminous efficiency of luminescent device and device lifetime.
The third object of the present invention is to provide a kind of organic electroluminescence device, and the organic electroluminescence device is using upper Blue light-emitting compound is stated as main substance so that the organic electroluminescence device has high efficiency and the superiority of long-life Energy.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
In a first aspect, the invention provides a kind of blue light-emitting compound, the structural formula of the compound are as follows：
Wherein, R1For in hydrogen, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical Any one,
R2For hydrogen, C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl Any one in base, pyrimidine radicals or triazine radical；
R3For appointing in hydrogen, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical Meaning is a kind of；
R4For hydrogen, C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl Any one in base, pyrimidine radicals or triazine radical.
As further preferably technical scheme, R1Phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl In base, pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C20 straight or branched alkyl, C3~C20 Cycloalkyl, C1~C20 alkoxy, halogen, cyano group, trifluoromethyl, Si (CH3)3Base or C6~C50 aryl are substituted.
As further preferably technical scheme, R2C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthalene In base, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C20 Straight or branched alkyl, C3~C24 cycloalkyl, C1~C20 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicane Base, naphthyl, anthryl, phenanthryl, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or atomicity are taken by 5~20 heteroaryl Generation.
As further preferably technical scheme, R3Phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, biphenyl In base, pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C20 straight or branched alkyl, C3~C12 Cycloalkyl, C1~C10 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicon substrate or C6~C30 aryl substituted.
As further preferably technical scheme, R4C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthalene In base, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C10 Straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicane Base, naphthyl, anthryl, phenanthryl, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or atomicity are taken by 5~20 heteroaryl Generation.
As further preferably technical scheme, the straight or branched alkyl of the C1~C20 is methyl, ethyl, propyl group, Isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl or n-octyl.
As further preferably technical scheme, the compound is any one in following compounds：
Second aspect, the invention provides a kind of application of blue light-emitting compound in luminescent device is prepared.
The third aspect, it is described the invention provides a kind of organic electroluminescence device, including anode, luminescent layer and negative electrode Luminescent layer includes above-mentioned blue light-emitting compound.
As further preferably technical scheme, be additionally provided between the anode and the luminescent layer hole injection layer and Hole transmission layer, electron transfer layer and electron injecting layer are additionally provided between the luminescent layer and the negative electrode.
Compared with prior art, beneficial effects of the present invention are：
Blue light-emitting compound provided by the invention can be used as blue-fluorescence material of main part, for organic electroluminescence device In can reduce driving voltage, improve luminous efficiency, brightness, heat endurance, color purity and device lifetime.
Blue light-emitting compound provided by the invention, which is applied to, to be prepared in luminescent device, it is possible to increase luminescent device lights Efficiency and device lifetime.
Organic electroluminescence device provided by the invention is using above-mentioned blue light-emitting compound as main substance so that should Organic electroluminescence device has the excellent properties of high efficiency and long-life.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment Condition person, the condition suggested according to normal condition or manufacturer are carried out.
In a kind of preferred embodiment of blue light-emitting compound provided by the invention, R1Phenyl, pyridine radicals, naphthalene In base, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C20 Straight or branched alkyl, C3~C20 cycloalkyl, C1~C20 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicane Base or C6~C50 aryl are substituted；
Wherein, C3~C20 cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
C1~C20 alkoxide is：The group that-OR is represented, the group that wherein R is represented is alkyl, alkyl be methyl, Ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive nonyl Base, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, N-heptadecane base, n-octadecane base, NSC 77136 base or n-eicosane base；
C6~C50 aryl be phenyl, 1- naphthyls, 2- naphthyls, 1- anthryls, 2- anthryls, 9- anthryls, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl, 1- aphthacenes base, 2- aphthacenes base, 9- aphthacenes base, 1- pyrenyls, 2- pyrenyls, 4- pyrenyls, 2- Xenyl, 3- xenyls, 4- xenyls, para-terpheny -4- bases, para-terpheny -3- bases, para-terpheny -2- bases, meta-terphenyl - 4- bases, meta-terphenyl -3- bases, meta-terphenyl -2- bases, o-tolyl, a tolyl, p-methylphenyl, to tert-butyl-phenyl, p- (2- phenyl propyls) phenyl, 3- methyl -2- naphthyls, 4- methyl isophthalic acids-naphthyl, 4- methyl isophthalic acids-anthryl, 4'- methyl biphenyls or 4 " - The tert-butyl group-para-terpheny -4- bases.
It is preferably carried out in one kind in mode, R2C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, In phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C20's Straight or branched alkyl, C3~C24 cycloalkyl, C1~C20 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicon substrate, Naphthyl, anthryl, phenanthryl, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or atomicity are substituted by 5~20 heteroaryl；
Wherein, C3~C24 cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
C1~C20 alkoxide is：The group that-OR is represented, the group that wherein R is represented is alkyl, alkyl be methyl, Ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive nonyl Base, positive decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, 18 Alkyl, nonadecyl or eicosyl；
The heteroaryl that atomicity is 5~20 is 1- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, pyridine radicals, 2- pyridine radicals, 3- Pyridine radicals, 4- pyridine radicals, 1- indyls, 2- indyls, 3- indyls, 4- indyls, 5- indyls, 6- indyls, 7- indoles Base, 1- isoindolyls, 2- isoindolyls, 3- isoindolyls, 4- isoindolyls, 5- isoindolyls, 6- isoindolyls, 7- iso-indoles Base, 2- furyls, 3- furyls, 2- benzofuranyls, 3- benzofuranyls, 4- benzofuranyls, 5- benzofuranyls, 6- benzene And the different benzo furan of furyl, 7- benzofuranyls, 1- isobenzofuran-bases, 3- isobenzofuran-bases, 4- isobenzofuran-bases, 5- Mutter base, 6- isobenzofuran-bases, 7- isobenzofuran-bases, 2- quinolyls, 3- quinolyls, 4- quinolyls, 5- quinolyls, 6- quinoline Base, 7- quinolyls, 8- quinolyls, 1- isoquinolyls, 3- isoquinolyls, 4- isoquinolyls, 5- isoquinolyls, 6- isoquinolyls, 7- isoquinolyls, 8- isoquinolyls, 2- quinoxalinyls, 5- quinoxalinyls, 6- quinoxalinyls, 1- coffee piperidinyl, 2- coffee piperidinyl, 3- coffee Piperidinyl, 4- coffee piperidinyl, 6- coffee piperidinyl, 7- coffee piperidinyl, 8- coffee piperidinyl, 9- coffee piperidinyl, 10- coffee piperidinyl, 1,7- phenanthrene cough up beautiful jade -2- bases, 1,7- phenanthrene coughs up beautiful jade -3- bases, 1,7- phenanthrene coughs up beautiful jade -4- bases, 1,7- phenanthrene coughs up beautiful jade -5- bases, 1,7- phenanthrene coughs up beautiful jade -6- bases, 1,7- phenanthrene coughs up beautiful jade -8- Base, 1,7- phenanthrene cough up beautiful jade -9- bases, 1,7- phenanthrene coughs up beautiful jade -10- bases, 1,8- phenanthrene coughs up beautiful jade -2- bases, 1,8- phenanthrene coughs up beautiful jade -3- bases, 1,8- phenanthrene is coughed up Beautiful jade -4- bases, 1,8- phenanthrene cough up beautiful jade -5- bases, 1,8- phenanthrene coughs up beautiful jade -6- bases, 1,8- phenanthrene coughs up beautiful jade -7- bases, 1,8- phenanthrene coughs up beautiful jade -9- bases, 1,8- Phenanthrene coughs up beautiful jade -10- bases, 1,9- phenanthrene coughs up beautiful jade -2- bases, 1,9- phenanthrene coughs up beautiful jade -3- bases, 1,9- phenanthrene coughs up beautiful jade -4- bases, 1,9- phenanthrene coughs up beautiful jade -5- bases, 1,9- phenanthrene coughs up beautiful jade -6- bases, 1,9- phenanthrene coughs up beautiful jade -7- bases, 1,9- phenanthrene coughs up beautiful jade -8- bases, 1,9- phenanthrene coughs up beautiful jade -10- bases, 1,10- phenanthrene cough up beautiful jade - 2- bases, 1,10- phenanthrene cough up beautiful jade -3- bases, 1,10- phenanthrene coughs up beautiful jade -4- bases, 1,10- phenanthrene coughs up beautiful jade -5- bases, 2,9- phenanthrolines -1- bases, 2,9- Phenanthrene coughs up beautiful jade -3- bases, 2,9- phenanthrene coughs up beautiful jade -4- bases, 2,9- phenanthrene coughs up beautiful jade -5- bases, 2,9- phenanthrene coughs up beautiful jade -6- bases, 2,9- phenanthrene coughs up beautiful jade -7- bases, 2,9- phenanthrene cough up beautiful jade -8- bases, 2,9- phenanthrene coughs up beautiful jade -10- bases, 2,8- phenanthrene coughs up beautiful jade -1- bases, 2,8- phenanthrene coughs up beautiful jade -3- bases, 2,8- phenanthrene cough up beautiful jade - 4- bases, 2,8- phenanthrene cough up beautiful jade -5- bases, 2,8- phenanthrene coughs up beautiful jade -6- bases, 2,8- phenanthrene coughs up beautiful jade -7- bases, 2,8- phenanthrene coughs up beautiful jade -9- bases, 2,8- phenanthrene is coughed up Beautiful jade -10- bases, 2,7- phenanthrene cough up beautiful jade -1- bases, 2,7- phenanthrene coughs up beautiful jade -3- bases, 2,7- phenanthrene coughs up beautiful jade -4- bases, 2,7- phenanthrene coughs up beautiful jade -5- bases, 2,7- Phenanthrene coughs up beautiful jade -6- bases, 2,7- phenanthrene coughs up beautiful jade -8- bases, 2,7- phenanthrene coughs up beautiful jade -9- bases, 2,7- phenanthrene coughs up beautiful jade -10- bases, 2- oxazolyls, 4- oxazoles Base, 5- oxazolyls, 2- oxadiazolyls, 5- oxadiazolyls, 3- furazanyls, 2- thienyls, 3- thienyls, 2- picoline -1- bases, 2- methylpyrrole -3- bases, 2- methylpyrrole -4- bases, 2- methylpyrrole -5- bases, 3- methylpyrrole -1- bases, 3- methylpyrroles -2- Base, 3- methylpyrrole -4- bases or 3- methylpyrrole -5- bases.
It is preferably carried out in one kind in mode, R3Phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, In pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C20 straight or branched alkyl, C3~C12 Cycloalkyl, C1~C10 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicon substrate or C6~C30 aryl are substituted；
Wherein, C3~C12 cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
C1~C10 alkoxide is：The group that-OR is represented, the group that wherein R is represented is alkyl, alkyl be methyl, Ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive nonyl Base or positive decyl；
C6~C30 aryl be phenyl, 1- naphthyls, 2- naphthyls, 1- anthryls, 2- anthryls, 9- anthryls, 1- phenanthryl, 2- phenanthryl, 3- phenanthryl, 4- phenanthryl, 9- phenanthryl, 1- aphthacenes base, 2- aphthacenes base, 9- aphthacenes base, 1- pyrenyls, 2- pyrenyls, 4- pyrenyls, 2- Xenyl, 3- xenyls, 4- xenyls, para-terpheny -4- bases, para-terpheny -3- bases, para-terpheny -2- bases, meta-terphenyl - 4- bases, meta-terphenyl -3- bases, meta-terphenyl -2- bases, o-tolyl, a tolyl, p-methylphenyl, to tert-butyl-phenyl, p- (2- phenyl propyls) phenyl, 3- methyl -2- naphthyls, 4- methyl isophthalic acids-naphthyl, 4- methyl isophthalic acids-anthryl, 4'- methyl biphenyls or 4 " - The tert-butyl group-para-terpheny -4- bases.
It is preferably carried out in one kind in mode, R4C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, In phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can be independently by C1~C10's Straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicon substrate, Naphthyl, anthryl, phenanthryl, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or atomicity are substituted by 5~20 heteroaryl；
Wherein, C3~C12 cycloalkyl is cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
C1~C10 alkoxide is：The group that-OR is represented, the group that wherein R is represented is alkyl, alkyl be methyl, Ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, positive nonyl Base or positive decyl；
The heteroaryl that atomicity is 5~20 is 1- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, pyridine radicals, 2- pyridine radicals, 3- Pyridine radicals, 4- pyridine radicals, 1- indyls, 2- indyls, 3- indyls, 4- indyls, 5- indyls, 6- indyls, 7- indoles Base, 1- isoindolyls, 2- isoindolyls, 3- isoindolyls, 4- isoindolyls, 5- isoindolyls, 6- isoindolyls, 7- iso-indoles Base, 2- furyls, 3- furyls, 2- benzofuranyls, 3- benzofuranyls, 4- benzofuranyls, 5- benzofuranyls, 6- benzene And the different benzo furan of furyl, 7- benzofuranyls, 1- isobenzofuran-bases, 3- isobenzofuran-bases, 4- isobenzofuran-bases, 5- Mutter base, 6- isobenzofuran-bases, 7- isobenzofuran-bases, 2- quinolyls, 3- quinolyls, 4- quinolyls, 5- quinolyls, 6- quinoline Base, 7- quinolyls, 8- quinolyls, 1- isoquinolyls, 3- isoquinolyls, 4- isoquinolyls, 5- isoquinolyls, 6- isoquinolyls, 7- isoquinolyls, 8- isoquinolyls, 2- quinoxalinyls, 5- quinoxalinyls, 6- quinoxalinyls, 1- coffee piperidinyl, 2- coffee piperidinyl, 3- coffee Piperidinyl, 4- coffee piperidinyl, 6- coffee piperidinyl, 7- coffee piperidinyl, 8- coffee piperidinyl, 9- coffee piperidinyl, 10- coffee piperidinyl, 1,7- phenanthrene cough up beautiful jade -2- bases, 1,7- phenanthrene coughs up beautiful jade -3- bases, 1,7- phenanthrene coughs up beautiful jade -4- bases, 1,7- phenanthrene coughs up beautiful jade -5- bases, 1,7- phenanthrene coughs up beautiful jade -6- bases, 1,7- phenanthrene coughs up beautiful jade -8- Base, 1,7- phenanthrene cough up beautiful jade -9- bases, 1,7- phenanthrene coughs up beautiful jade -10- bases, 1,8- phenanthrene coughs up beautiful jade -2- bases, 1,8- phenanthrene coughs up beautiful jade -3- bases, 1,8- phenanthrene is coughed up Beautiful jade -4- bases, 1,8- phenanthrene cough up beautiful jade -5- bases, 1,8- phenanthrene coughs up beautiful jade -6- bases, 1,8- phenanthrene coughs up beautiful jade -7- bases, 1,8- phenanthrene coughs up beautiful jade -9- bases, 1,8- Phenanthrene coughs up beautiful jade -10- bases, 1,9- phenanthrene coughs up beautiful jade -2- bases, 1,9- phenanthrene coughs up beautiful jade -3- bases, 1,9- phenanthrene coughs up beautiful jade -4- bases, 1,9- phenanthrene coughs up beautiful jade -5- bases, 1,9- phenanthrene coughs up beautiful jade -6- bases, 1,9- phenanthrene coughs up beautiful jade -7- bases, 1,9- phenanthrene coughs up beautiful jade -8- bases, 1,9- phenanthrene coughs up beautiful jade -10- bases, 1,10- phenanthrene cough up beautiful jade - 2- bases, 1,10- phenanthrene cough up beautiful jade -3- bases, 1,10- phenanthrene coughs up beautiful jade -4- bases, 1,10- phenanthrene coughs up beautiful jade -5- bases, 2,9- phenanthrolines -1- bases, 2,9- Phenanthrene coughs up beautiful jade -3- bases, 2,9- phenanthrene coughs up beautiful jade -4- bases, 2,9- phenanthrene coughs up beautiful jade -5- bases, 2,9- phenanthrene coughs up beautiful jade -6- bases, 2,9- phenanthrene coughs up beautiful jade -7- bases, 2,9- phenanthrene cough up beautiful jade -8- bases, 2,9- phenanthrene coughs up beautiful jade -10- bases, 2,8- phenanthrene coughs up beautiful jade -1- bases, 2,8- phenanthrene coughs up beautiful jade -3- bases, 2,8- phenanthrene cough up beautiful jade - 4- bases, 2,8- phenanthrene cough up beautiful jade -5- bases, 2,8- phenanthrene coughs up beautiful jade -6- bases, 2,8- phenanthrene coughs up beautiful jade -7- bases, 2,8- phenanthrene coughs up beautiful jade -9- bases, 2,8- phenanthrene is coughed up Beautiful jade -10- bases, 2,7- phenanthrene cough up beautiful jade -1- bases, 2,7- phenanthrene coughs up beautiful jade -3- bases, 2,7- phenanthrene coughs up beautiful jade -4- bases, 2,7- phenanthrene coughs up beautiful jade -5- bases, 2,7- Phenanthrene coughs up beautiful jade -6- bases, 2,7- phenanthrene coughs up beautiful jade -8- bases, 2,7- phenanthrene coughs up beautiful jade -9- bases, 2,7- phenanthrene coughs up beautiful jade -10- bases, 2- oxazolyls, 4- oxazoles Base, 5- oxazolyls, 2- oxadiazolyls, 5- oxadiazolyls, 3- furazanyls, 2- thienyls, 3- thienyls, 2- picoline -1- bases, 2- methylpyrrole -3- bases, 2- methylpyrrole -4- bases, 2- methylpyrrole -5- bases, 3- methylpyrrole -1- bases, 3- methylpyrroles -2- Base, 3- methylpyrrole -4- bases or 3- methylpyrrole -5- bases.
Blue light-emitting compound provided by the invention is further described in detail with reference to embodiment 1-6.
Embodiment 1
A kind of blue light-emitting compound
Compound 2 is prepared by following methods：
The synthesis of intermediate -1
[reaction equation 1]
In 1L three-necked flask, input 25.4g (100mmol) 2- benzene is luxuriant and rich with fragrance, is dissolved with 500ml glacial acetic acid, dripped at room temperature Add 63.9g Br2(400mml).120 DEG C are warming up to after completion of dropwise addition, backflow 18 hours overnight.Question response terminates, and adds saturation Na2SO3Solution, after stirring 1 hour, solid is formed, is filtered, filter cake is rinsed with water, then, first is used after drying with alcohol flushing once Benzene and ethyl alcohol recrystallization, obtain 36.7g intermediate -1, yield 89%.
The synthesis of intermediate -2
[reaction equation 2]
Intermediate -1 and 21.9g (98mmol) 6- that 36.7g (89.1mmol) is added in dry 2L three-necked flasks are bromo- 1- hydroxyl naphthalenes, make solvent with 800ml DMF, stir logical nitrogen 15 minutes, add 0.6g (3%mol) Pd (OAc)2, 1.4g (6%mol) PPh3, finally it is slowly added to 87.1g (267.3mmol) Cs2CO3, 160 DEG C are warming up to, is flowed back 24 hours.Question response Terminate, be cooled to room temperature, add activated carbon, cross short column of silica gel, filtrate toluene and water extraction, washing organic phase 4 times, rotation is except molten Agent, with toluene and ethyl alcohol recrystallization, obtain 33.3g intermediate -2, yield 79%.
The synthesis of compound 2
[reaction equation 3]
33.3g (70.4mmol) intermediates -2 and 9.4g (77.4mmol) phenyl boric acid are added in 2L three-necked flask, 600ml toluene and the dissolving of 150ml ethanol are added, leads to nitrogen 15 minutes, adds 106ml K2CO3The water of (211.2mmol, 2M) Solution, it is eventually adding 1.6g Pd (PPh3) 4 (2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add charcoal absorption, Filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 28.5g compounds 2, yield is 86%.
1H NMR(DMSO,300Hz):δ (ppm)=9.26-9.01 (m, 2H), 8.62-8.40 (s, 1H), 8.38-8.21 (d,1H),8.19-8.04(d,1H),8.02-7.86(m,2H),7.83-7.46(m,H),7.42-7.07(m,8H),6.74- 6.46(d,1H)
MS(FAB):470(M+)
Embodiment 2
A kind of blue light-emitting compound
Compound 24 is prepared by following methods：
The synthesis of intermediate -1
[reaction equation 4]
In 1L three-necked flask, input 25.4g (100mmol) 2- benzene is luxuriant and rich with fragrance, is dissolved with 500ml glacial acetic acid, dripped at room temperature Add 63.9g Br2(400mml).120 DEG C are warming up to after completion of dropwise addition, is flowed back 18 hours.Question response terminates, and adds saturation Na2SO3 Solution, after stirring 1 hour, solid is formed, is filtered, filter cake is rinsed with water, then, toluene and second is used after drying with alcohol flushing once Alcohol recrystallizes, and obtains 36.7g intermediate -1, yield 89%.
The synthesis of intermediate -2
[reaction equation 5]
Intermediate -1 and 21.9g (98mmol) 6- that 36.7g (89.1mmol) is added in dry 2L three-necked flasks are bromo- 1- hydroxyl naphthalenes, make solvent with 800ml DMF, stir logical nitrogen 15 minutes, add 0.6g (3%mol) Pd (OAc)2, 1.4g (6%mol) PPh3, finally it is slowly added to 87.1g (267.3mmol) Cs2CO3, 160 DEG C are warming up to, is flowed back 24 hours.Question response Terminate, be cooled to room temperature, add activated carbon, cross short column of silica gel, filtrate toluene and water extraction, washing organic phase 4 times, rotation is except molten Agent, with toluene and ethyl alcohol recrystallization, obtain 33.3g intermediate -2, yield 79%.
The synthesis of intermediate -3
[reaction equation 6]
33.3g (70.3mmol) intermediate -2 is put into 2L three-necked flask, makees solvent with 600ml DMF, then 13.8g (77.4mmol) NBS is added under the conditions of room temperature lucifuge, room temperature lucifuge is reacted 18 hours.Question response terminates, and adds saturation Na2SO3Solution separates out solid, stirs 1 hour, filters, is repeatedly rinsed with water, then with alcohol flushing 1 time, after drying with toluene and Ethyl alcohol recrystallization, obtain 35.3g intermediate -3, yield 91%.
The synthesis of intermediate -4
[reaction equation 7]
35.3g (64mmol) intermediate -3 and 8.6g (77.4mmol) phenyl boric acid are added in 2L three-necked flask, 700ml toluene and the dissolving of 150ml ethanol are added, leads to nitrogen 15 minutes, adds 64ml K2CO3(128mmol, 2M's) is water-soluble Liquid, it is eventually adding 1.5g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add charcoal absorption, take out Filter, rotation remove solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 22.9g intermediate -4, yield is 65%.
The synthesis of compound 24
[reaction equation 8]
By 22.9g (41.6mmol) intermediate -4 and 7.9g (45.8mmol) 2- naphthalene boronic acids, be added to 1L three mouthfuls burn In bottle, 400ml toluene and the dissolving of 100ml ethanol are added, leads to nitrogen 15 minutes, adds 62ml K2CO3(124.8mmol,2M) The aqueous solution, be eventually adding 1.0g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Activated carbon is added to inhale It is attached, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 21.8g compounds 24, yield is 88%.
1H NMR(DMSO,300Hz):δ (ppm)=9.26-9.01 (m, 2H), 8.62-8.40 (s, 1H), 8.35-8.01 (m,6H),7.99-7.81(s,1H),7.78-7.51(m,9H),7.49-7.15(m,9H)
MS(FAB):596(M+)
Embodiment 3
A kind of blue light-emitting compound
Compound 36 is prepared by following methods：
The synthesis of intermediate -5
[reaction equation 9]
25.7g (100mmol) 4- bromines phenanthrene and 18.9g (110mmol) 1- naphthalene boronic acids are added in 1L three-necked flask, 500ml toluene and the dissolving of 125ml ethanol are added, leads to nitrogen 15 minutes, adds 150ml K2CO3(300mmol, 2M's) is water-soluble Liquid, it is eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add charcoal absorption, take out Filter, rotation remove solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 28g intermediate -5, yield is 92%.
The synthesis of intermediate -6
[reaction equation 10]
28g (92mmol) intermediate -5 is put into 2L three-necked flask, makees solvent with 600ml DMF, then in room 18g (101.2mmol) NBS is added under the conditions of warm lucifuge, room temperature lucifuge is reacted 18 hours.Question response terminates, and adds saturation Na2SO3 Solution separates out solid, stirs 1 hour, filters, is repeatedly rinsed with water, then with alcohol flushing 1 time, toluene and ethanol weight are used after drying Crystallization, obtains 29.3g intermediate -6, yield 82%.
The synthesis of intermediate -7
[reaction equation 11]
Experimental provision is fully dried, 29.3g (76.4mmol) intermediate -6 are added in 2L three-necked flasks, are added 600ml is dried to obtain tetrahydrofuran, and -78 DEG C are cooled to after dissolving, 33.6ml 2.5M n-BuLi is added dropwise.After completion of dropwise addition Stir 1 hour at this temperature, then 10.3g trimethylborates (1.3eq.) are added dropwise at such a temperature, be stirred at room temperature after completion of dropwise addition 12 hours.Question response terminates, and adds 4M hydrochloric acid solutions, is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, does Dry, rotation remove solvent, and obtained crude product is boiled with ethyl acetate, and filtering, filter cake is boric acid product, 22.6g intermediate -7, is produced Rate is 85%.
The synthesis of intermediate -8
[reaction equation 12]
By the bromo- 1- hydroxyl naphthalenes of 22.3g (100mmol) 3- and 18.9g (110mmol) 1- naphthalene boronic acids, three mouthfuls of 1L are added to In flask, 400ml toluene and the dissolving of 100ml ethanol are added, leads to nitrogen 15 minutes, adds 150ml K2CO3(300mmol,2M) The aqueous solution, be eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Activated carbon is added to inhale It is attached, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 24.6g intermediate -8, yield is 91%.
The synthesis of intermediate -9
[reaction equation 13]
In 1L three-necked flask, input 25.7g (100mmol) 2- bromines are luxuriant and rich with fragrance, are dissolved with 500ml glacial acetic acid, dripped at room temperature Add 63.9g Br2(400mml).120 DEG C are warming up to after completion of dropwise addition, backflow 18 hours overnight.Question response terminates, and adds saturation Na2SO3Solution, after stirring 1 hour, solid is formed, is filtered, filter cake is rinsed with water, then, first is used after drying with alcohol flushing once Benzene and ethyl alcohol recrystallization, obtain 35.7g intermediate -9, yield 86%.
The synthesis of intermediate -10
[reaction equation 14]
Added in dry 2L three-necked flasks in 34.3g (82.7mmol) intermediate -9 and 24.6g (91mmol) Mesosome -8, make solvent with 600ml DMF, stir logical nitrogen 15 minutes, add 0.56g (3%mol) Pd (OAc)2, 1.3g (6%mol) PPh3, finally it is slowly added to 80.8g (248.1mmol) Cs2CO3, 160 DEG C are warming up to, is flowed back 24 hours.Question response Terminate, be cooled to room temperature, add activated carbon, cross short column of silica gel, filtrate toluene and water extraction, washing organic phase 4 times, rotation is except molten Agent, with toluene and ethyl alcohol recrystallization, obtain 31.2g intermediate -10, yield 72%.
The synthesis of intermediate -11
[reaction equation 15]
Experimental provision is fully dried, 31.2g (59.5mmol) intermediate -10 are added in 2L three-necked flasks, are added 600ml is dried to obtain tetrahydrofuran, -78 DEG C is cooled to after dissolving, the THF that 31.3ml 2M LDA (62.5mmol) is added dropwise is molten Liquid.Stirred at such a temperature after completion of dropwise addition 1 hour, then add 16.6g iodine (65.5eq.) at such a temperature, after completion of dropwise addition It is stirred at room temperature 12 hours.Question response terminates, and adds 4M hydrochloric acid solutions, is extracted with dichloromethane, organic phase is washed with saturated common salt To neutrality, dry, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 30.9g intermediate -11, yield 80%.
The synthesis of intermediate -12
[reaction equation 16]
By 30.9g (47.6mmol) intermediate -11 and 15.6g (52.4mmol) 9- (3- phenyl boric acids) anthracene, 2L is added to Three-necked flask in, add 600ml toluene and the dissolving of 150ml ethanol, lead to nitrogen 15 minutes, add 72ml K2CO3 The aqueous solution of (142.8mmol, 2M), it is eventually adding 1.1g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Add charcoal absorption, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 34g intermediate -12, yield exists 92%.
The synthesis of compound 36
[reaction equation 17]
By 34g (43.8mmol) intermediate -12 and 16.8g (48.2mmol) 9- (3- phenyl boric acids) anthracene, it is added to 2L's In three-necked flask, 600ml toluene and the dissolving of 150ml ethanol are added, leads to nitrogen 15 minutes, adds 66ml K2CO3 The aqueous solution of (131.4mmol, 2M), it is eventually adding 1.0g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Add charcoal absorption, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 39g compounds 36, yield exists 89%.
1H NMR(DMSO,300Hz):δ (ppm)=9.26-8.86 (m, 6H), 8.54-8.35 (m, 5H), 8.32-8.19 (m,6H),8.17-7.95(m,4H),7.93-7.81(m,3H),7.78-7.32(m,21H),7.24-7.02(s,1H)
MS(FAB):999(M+)
Embodiment 4
A kind of blue light-emitting compound
Compound 67 is prepared by following methods：
The synthesis of intermediate -13
[reaction equation 18]
33.6g (100mmol) 9,10- dibromos phenanthrene and 24.5g (110mmol) 2- are added in dry 2L three-necked flasks Bromo- 1- naphthols, make solvent with 600ml DMF, stir logical nitrogen 15 minutes, add 0.67g (3%mol) Pd (OAc)2,1.6g (6%mol) PPh3, finally it is slowly added to 97.7g (300mmol) Cs2CO3, 160 DEG C are warming up to, is flowed back 24 hours.Question response knot Beam, room temperature is cooled to, adds activated carbon, cross short column of silica gel, filtrate toluene and water extraction, washing organic phase 4 times, rotation is except molten Agent, with toluene and ethyl alcohol recrystallization, obtain 31g intermediate -13, yield 78%.
The synthesis of compound 67
[reaction equation 19]
By 31g (78mmol) intermediate -13 and 17g (85.8mmol) 2- biphenylboronic acids, 2L three-necked flask is added to In, 600ml toluene and the dissolving of 150ml ethanol are added, leads to nitrogen 15 minutes, adds 117ml K2CO3The water of (234mmol, 2M) Solution, it is eventually adding 1.8g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add charcoal absorption, take out Filter, rotation remove solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 31.2g compounds 67, yield is 85%.
1H NMR(DMSO,300Hz):δ (ppm)=9.26-9.01 (d, 1H), 8.97-8.84 (d, 1H), 8.62-8.40 (d,1H),8.38-8.06(m,4H),8.01-7.86(m,2H),7.83-7.23(m,13H)
MS(FAB):470(M+)
Embodiment 5
A kind of blue light-emitting compound
Compound 92 is prepared by following methods：
The synthesis of intermediate -9
[reaction equation 20]
In 1L three-necked flask, input 25.4g (100mmol) 2- bromines are luxuriant and rich with fragrance, are dissolved with 500ml glacial acetic acid, dripped at room temperature Add 63.9g Br2(400mml).120 DEG C are warming up to after completion of dropwise addition, backflow 18 hours overnight.Question response terminates, and adds saturation Na2SO3Solution, after stirring 1 hour, solid is formed, is filtered, filter cake is rinsed with water, then, first is used after drying with alcohol flushing once Benzene and ethyl alcohol recrystallization, obtain 35.7g intermediate -9, yield 86%.
The synthesis of intermediate -14
[reaction equation 21]
By the bromo- 5- hydroxyl naphthalenes of 22.3g (100mmol) 2- and 18.9g (110mmol) 1- naphthalene boronic acids, three mouthfuls of 1L are added to In flask, 400ml toluene and the dissolving of 100ml ethanol are added, leads to nitrogen 15 minutes, adds 150ml K2CO3(300mmol,2M) The aqueous solution, be eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Activated carbon is added to inhale It is attached, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 23.8g intermediate -14, yield is 88%.
The synthesis of intermediate -15
[reaction equation 22]
33.2g (80mmol) intermediate -9 and 23.8g (88mmol) centre are added in dry 2L three-necked flasks Body -14, make solvent with 600ml DMF, stir logical nitrogen 15 minutes, add 0.54g (3%mol) Pd (OAc)2, 1.3g (6% mol)PPh3, finally it is slowly added to 78.2g (240mmol) Cs2CO3, 160 DEG C are warming up to, is flowed back 24 hours.Question response terminates, cold But to room temperature, activated carbon is added, crosses short column of silica gel, filtrate toluene and water extraction, washing organic phase 4 times, rotation removes solvent, uses first Benzene and ethyl alcohol recrystallization, obtain 31.4g intermediate -15, yield 75%.
The synthesis of compound 92
[reaction equation 23]
By 31.4g (60mmol) intermediate -15 and 18.9g (66mmol) 3- (9H- carbazole -9- bases) phenyl boric acid, add Into 2L three-necked flask, 600ml toluene and the dissolving of 150ml ethanol are added, leads to nitrogen 15 minutes, adds 90ml K2CO3 The aqueous solution of (180mmol, 2M), it is eventually adding 1.4g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Add charcoal absorption, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 33.7g compounds 92, yield 82%.
1H NMR(DMSO,300Hz):δ (ppm)=9.26-9.01 (m, 2H), 8.97-8.89 (d, 1H), 8.71-8.59 (d,1H),8.56-8.32(m,3H),8.29-8.09(m,5H),8.06-7.86(m,2H),7.83-7.35(m,15H),7.32- 7.07(t,1H),6.61-6.32(d,1H)
MS(FAB):685(M+)
Embodiment 6
A kind of blue light-emitting compound
Compound 114 is prepared by following methods：
The synthesis of intermediate -16
[reaction equation 24]
In 2L three-necked flask, input 30.4g (100mmol) 2- iodine is luxuriant and rich with fragrance, is dissolved with 600ml glacial acetic acid, dripped at room temperature Add 63.9g Br2(400mml).120 DEG C are warming up to after completion of dropwise addition, backflow 18 hours overnight.Question response terminates, and adds saturation Na2SO3Solution, solid is formed, after stirring 1 hour, filtered, filter cake is rinsed with water, then, first is used after drying with alcohol flushing once Benzene and ethyl alcohol recrystallization, obtain 37.4g intermediate -16, yield 81%.
The synthesis of intermediate -17
[reaction equation 25]
37.4g (81mmol) intermediate -16 and 19.9g (89.1mmol) 2- is added in dry 2L three-necked flasks Bromo- 1- naphthols, make solvent with 800ml DMF, stir logical nitrogen 15 minutes, add 0.55g (3%mol) Pd (OAc)2,1.3g (6%mol) PPh3, finally it is slowly added to 79.2g (243mmol) Cs2CO3, 160 DEG C are warming up to, is flowed back 24 hours.Question response knot Beam, room temperature is cooled to, adds activated carbon, cross short column of silica gel, filtrate toluene and water extraction, washing organic phase 4 times, rotation is except molten Agent, with toluene and ethyl alcohol recrystallization, obtain 32.2g intermediate -17, yield 76%.
The synthesis of intermediate -18
[reaction equation 26]
25.8g (100mmol) 4- bromines phenanthridines and 23.3g (110mmol) dibenzofurans -4- boric acid, are added to the three of 2L In mouth flask, 500ml toluene and the dissolving of 125ml ethanol are added, leads to nitrogen 15 minutes, adds 150ml K2CO3(300mmol, Aqueous solution 2M), it is eventually adding 2.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add activated carbon Absorption, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 29.4g intermediate -18, yield is 85%.
The synthesis of intermediate -19
[reaction equation 27]
29.4g (85mmol) intermediate -18 is put into 2L three-necked flask, makees solvent with 600ml DMF, then in room 16.6g (93.5mmol) NBS is added under the conditions of warm lucifuge, room temperature lucifuge is reacted 18 hours.Question response terminates, and adds saturation Na2SO3Solution separates out solid, stirs 1 hour, filters, is repeatedly rinsed with water, then with alcohol flushing 1 time, after drying with toluene and Ethyl alcohol recrystallization, obtain product 27g intermediate -19, yield 75%.
The synthesis of intermediate -20
[reaction equation 28]
Experimental provision is fully dried, 24.9g (63.8mmol) intermediate -19 are added in 2L three-necked flasks, are added 600ml is dried to obtain tetrahydrofuran, and -78 DEG C are cooled to after dissolving, 28.1ml 2.5M n-BuLi is added dropwise.After completion of dropwise addition Stir 1 hour at this temperature, then 8.6g trimethylborates (1.3eq.) are added dropwise at such a temperature, 12 are stirred at room temperature after completion of dropwise addition Hour.Question response terminates, and adds 4M hydrochloric acid solutions, is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, does Dry, rotation remove solvent, boils obtained crude product with ethyl acetate, filters, and filter cake is boric acid product, 20.4g intermediate -20, Yield is 82%.
The synthesis of intermediate -21
[reaction equation 29]
24.9g (47.6mmol) intermediates -17 and 20.4g (52.4mmol) intermediate -20, it is added to 2L three-necked flask In, 500ml toluene and the dissolving of 125ml ethanol are added, leads to nitrogen 15 minutes, adds 71ml K2CO3(142.8mmol, 2M's) The aqueous solution, it is eventually adding 1.1g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add charcoal absorption, Filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 29.3g intermediate -21, yield is 83%.
The synthesis of intermediate -22
[reaction equation 30]
29.3g (39.5mmol) intermediates -21 and 5.3g (43.5mmol) phenyl boric acid, are added in 2L three-necked flask, 600ml toluene and the dissolving of 150ml ethanol are added, leads to nitrogen 15 minutes, adds 59.3ml K2CO3The water of (118.5mmol, 2M) Solution, it is eventually adding 0.91g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 12 hours.Add charcoal absorption, Filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 25.3g intermediate -22, yield is 87%.
The synthesis of intermediate -23
[reaction equation 31]
25.3g (34.2mmol) intermediate -22 is put into 2L three-necked flask, makees solvent with 500ml DMF, then 6.7g (37.6mmol) NBS is added under the conditions of room temperature lucifuge, room temperature lucifuge is reacted 18 hours.Question response terminates, and adds saturation Na2SO3Solution separates out solid, stirs 1 hour, filters, is repeatedly rinsed with water, then with alcohol flushing 1 time, after drying with toluene and Ethyl alcohol recrystallization, obtain product 22.3g intermediate -23, yield 80%.
The synthesis of compound 114
[reaction equation 32]
22.3g (27.4mmol) intermediate -23 and 5.3g (43.5mmol) 3- (9H- carbazole -9- bases) phenyl boric acid, add Into 1L three-necked flask, 400ml toluene and the dissolving of 100ml ethanol are added, leads to nitrogen 15 minutes, adds 41.1ml K2CO3 The aqueous solution of (82.2mmol, 2M), it is eventually adding 0.63g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reacts 12 hours and ties Beam.Add charcoal absorption, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 21.7g compounds 114, yield 81%.
1H NMR(DMSO,300Hz):δ (ppm)=9.26-9.01 (m, 2H), 8.91-8.76 (s, 1H), 8.71-8.43 (m,2H),8.41-8.15(m,4H),8.11-7.35(m,31H),7.23-7.07(m,2H)
MS(FAB):979(M+)
Using above-mentioned reaction equation 1-32 method, above-claimed cpd 1-120 can be synthesized.
The structure of the organic electroluminescence device of the present invention is typical but is not limited to following several：
(1) anode/luminescent layer/negative electrode；
(2) anode/hole injection layer/luminescent layer/negative electrode；
(3) anode/hole injection layer/hole transmission layer/luminescent layer/negative electrode；
(4) anode/hole injection layer/hole transmission layer/electron-blocking layer/luminescent layer/negative electrode；
(5) anode/luminescent layer/electron injecting layer/negative electrode；
(6) anode/luminescent layer/electron transfer layer/electron injecting layer/negative electrode；
(7) anode/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/negative electrode；
(8) anode/hole injection layer/hole transmission layer/luminescent layer/electron transfer layer/electron injecting layer/negative electrode；
(9) anode/hole injection layer/hole transmission layer/electron-blocking layer/luminescent layer/hole blocking layer/electric transmission Layer/electron injecting layer/negative electrode/coating.
Manufacture method for structure for the organic electroluminescence device of (8), comprises the following steps：
Step 1, anode material is crossed into modeling and forms anode in substrate surface, used substrate selection has good clear Property, the glass substrate or transparent plastic substrate of surface smoothness, operability and water proofing property, anode material can use transparent and pass The property led superior ITO, IZO, SnO2, ZnO etc..
Step 2, by hole injection layer material (HIL) vacuum heat deposition or anode surface is spin-coated on, hole injection layer material Can be CuPc, m-MTDATA, m-MTDAPB, TCTA, 2-TNATA of star-like amine or from Japanese Idemitsu Kosen Co., Ltd.'s energy IDE406 enough bought etc..
Step 3, by hole transport layer material (HTL) vacuum heat deposition or be spin-coated on hole injection layer surface formed hole pass Defeated layer.Hole transport layer material can be α-NPD, NPB or TPD.
Step 4, by emitting layer material (EML) vacuum heat deposition or hole transport layer surface is spin-coated on, forms luminescent layer.Institute The emitting layer material used is to form main substance, and the blue phosphor to match with it by the blue light-emitting compound of the present invention Dopant doping forms.
Step 5, by electron transport layer materials (ETL) vacuum heat deposition or it is spin-coated on luminous layer surface and forms electric transmission Layer.There is no particular limitation for electron transport layer materials, preferably using Alq3.
Step 6, by electron injecting layer material (EIL) vacuum heat deposition or electric transmission layer surface is spin-coated on, forms electronics Implanted layer.Electron injecting layer material can be LiF, Liq, Li2O, BaO, NaCl, CsF etc..
Step 7, by cathode material vacuum heat deposition or electron injecting layer is spin-coated on, forms negative electrode.Cathode material, Ke Yiwei Li, Al, Al-Li, Ca, Mg, Mg-In, Mg-Ag etc..Alternatively, it is also possible to be made using tin indium oxide (ITO) or indium zinc oxide (IZO) Into light transmissive transparent cathode.
Further, hole blocking layer (HBL) can also be added between luminescent layer and electron transfer layer, while luminous Layer is used together phosphorescence doping, it is possible to achieve prevents triplet excitons or hole to be diffused into the effect of electron transfer layer.By hole Barrier material (HBL) vacuum heat deposition is spin-coated on luminous layer surface, forms hole blocking layer.Hole blocking layer material does not have Special to limit, preferably Liq, 2- methyl -8-hydroxyquinoline parazon close aluminium, BCP and LiF etc..
Further, luminescent layer is the blue-light-emitting main substance and dopant of the present invention and appointing in addition to the present invention What it is existing it is known luminescent material is laminated forms, as long as without prejudice to reaching the respective objects of the present invention.
Organic electroluminescence device provided by the invention is done further in detail with reference to embodiment 7-17 and reference examples 1 Explanation.
Embodiment 7
A kind of organic electroluminescence device, including set gradually anode, hole injection layer, hole transmission layer, luminescent layer, Electron transfer layer, electron injecting layer, negative electrode and coating, the luminescent layer include main substance and dopant species, the master Body material is the compound 2 that embodiment 1 provides.
Above-mentioned organic electroluminescence device is prepared by following steps：On the substrate in existing reflecting layer, ITO sun is formed Pole, use N2Ion or UV-Ozone are surface-treated.On herein, steamed by the use of HAT-CN as hole injection layer (HIL) material Plate 10nm thickness.Next on above-mentioned hole injection layer top, select NPD to carry out vacuum evaporation, form the sky of 120nm thickness Cave transport layer.In luminescent layer (EML) above above-mentioned hole transmission layer, in the compound with the present invention, compound 2 is selected to make 25nm thickness is deposited for main substance, while uses t-Bu-Perylene as dopant doping about 5% or so.Herein it On with 1:Derivative and Liq of 1 weight than mixing anthracene, are deposited the electron transfer layer (ETL) of 35nm thickness, are deposited above it 2nm Liq is as electron injecting layer (EIL).Afterwards, 9 are pressed with magnesium (Mg) and silver-colored (Ag):The mixture that 1 ratio is mixed As cathode evaporation 15nm thickness, the evaporation 65nm N4, N4 '-bis- [4- [double (3- aminomethyl phenyls) ammonia] above above-mentioned negative electrode Phenyl]-N4, N4 '-hexichol-[1,1 '-biphenyl] -4,4 '-diamines (DNTPD) is used as coating (CPL).Finally, used on its paper Sealed containing UV curable adhesives absorbent material, to protect organic electroluminescence device not by the oxygen in air or moisture institute Influence.
The structural formula of involved compound is as follows in the present embodiment：
Embodiment 8~17
Respectively using compound 13,24,28,36,48,67,73,81,92 and 114 as the main substance in blue EML, Other parts are consistent with embodiment 7, produce the organic electroluminescence device of embodiment 8~17 accordingly.
Reference examples 1
Difference with embodiment 7 is, the compound conduct of the present invention is replaced using (2- naphthyls) anthracenes of 9,10- bis- (ADN) Blue light main substance, remaining is same as Example 7.
The organic electroluminescence device that embodiment 7~17 and reference examples 1 are prepared is in current density 10mA/cm2's Under the conditions of carry out performance test, it is as a result as shown in the table.
As can be known from the above table, the Organic Electricity prepared using compound of the present invention as the blue light main substance of luminescent layer Compared with reference examples, luminous efficiency significantly improves the embodiment 7~17 of electroluminescence device, and highest can improve 58.5%, driving electricity Pressure is obvious to be reduced.In addition, from the point of view of the result of measure chromaticity coordinates (CIE (X Y)), compared with reference examples 1, in embodiment 7~17, Chromaticity coordinates CIE Y value is lower, therefore can confirm that this material has the feature of dark blue (deep blue).Therefore, indigo plant of the invention Main substance of the color luminophor as luminescent layer in organic electroluminescence device, the driving voltage of device can be made to reduce, imitate Rate increase, and there is dark blue characteristic.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims Including belonging to all such changes and modifications in the scope of the invention.

Claims (10)

1. a kind of blue light-emitting compound, it is characterised in that the structural formula of the compound is as follows：
Wherein, R1For appointing in hydrogen, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical Meaning is a kind of；
R2For hydrogen, C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, phonetic Any one in piperidinyl or triazine radical；
R3To be any one in hydrogen, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical Kind；
R4For hydrogen, C1~C20 straight or branched alkyl, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, phonetic Any one in piperidinyl or triazine radical.
2. blue light-emitting compound according to claim 1, it is characterised in that R1Phenyl, pyridine radicals, naphthyl, phenanthryl, In anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can independently by C1~C20 straight chain or Branched alkyl, C3~C20 cycloalkyl, C1~C20 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicon substrate or C6~ C50 aryl is substituted.
3. blue light-emitting compound according to claim 1, it is characterised in that R2C1~C20 straight or branched alkane In base, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can With independently by C1~C20 straight or branched alkyl, C3~C24 cycloalkyl, C1~C20 alkoxy, halogen, cyano group, Trifluoromethyl, trimethyl silicon substrate, naphthyl, anthryl, phenanthryl, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or atomicity are 5 ~20 heteroaryl is substituted.
4. blue light-emitting compound according to claim 1, it is characterised in that R3Phenyl, pyridine radicals, naphthyl, phenanthryl, In anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can independently by C1~C20 straight chain or Branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, cyano group, trifluoromethyl, trimethyl silicon substrate or C6~ C30 aryl is substituted.
5. blue light-emitting compound according to claim 1, it is characterised in that R4C1~C20 straight or branched alkane In base, phenyl, pyridine radicals, naphthyl, phenanthryl, anthryl, phenanthridinyl, xenyl, pyrimidine radicals or triazine radical, at least one hydrogen atom can With independently by C1~C10 straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, cyano group, Trifluoromethyl, trimethyl silicon substrate, naphthyl, anthryl, phenanthryl, dibenzofuran group, fluorenyl, carbazyl, Spirofluorene-based or atomicity are 5 ~20 heteroaryl is substituted.
6. according to the blue light-emitting compound described in claim any one of 1-5, it is characterised in that the straight chain of the C1~C20 Or branched alkyl be methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, N-heptyl or n-octyl.
7. blue light-emitting compound according to claim 1, it is characterised in that the compound is in following compounds Any one：
8. application of the blue light-emitting compound described in claim any one of 1-7 in luminescent device is prepared.
9. a kind of organic electroluminescence device, it is characterised in that including anode, luminescent layer and negative electrode, the luminescent layer includes Blue light-emitting compound described in claim any one of 1-7.
10. organic electroluminescence device according to claim 9, it is characterised in that the anode and the luminescent layer it Between be additionally provided with hole injection layer and hole transmission layer, be additionally provided between the luminescent layer and the negative electrode electron transfer layer and Electron injecting layer.
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