CN107686484A - Organic electroluminescent compounds and the organic electroluminescence device using the compound - Google Patents

Organic electroluminescent compounds and the organic electroluminescence device using the compound Download PDF

Info

Publication number
CN107686484A
CN107686484A CN201610635159.XA CN201610635159A CN107686484A CN 107686484 A CN107686484 A CN 107686484A CN 201610635159 A CN201610635159 A CN 201610635159A CN 107686484 A CN107686484 A CN 107686484A
Authority
CN
China
Prior art keywords
added
toluene
compound
reaction
synthesis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610635159.XA
Other languages
Chinese (zh)
Inventor
金振禹
钱超
高鹏惠
王晓维
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Topto Materials Co Ltd
Original Assignee
Nanjing Topto Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Topto Materials Co Ltd filed Critical Nanjing Topto Materials Co Ltd
Priority to CN201610635159.XA priority Critical patent/CN107686484A/en
Publication of CN107686484A publication Critical patent/CN107686484A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Abstract

A kind of organic electroluminescence device the invention provides organic electroluminescent compounds and using the compound, the structural formula of compound is as shown in formula I：

Description

Organic electroluminescent compounds and the organic electroluminescence device using the compound
Technical field
The invention belongs to luminescent material technical field, and in particular to a kind of organic electroluminescent compounds and use the chemical combination The organic electroluminescence device of thing.
Background technology
So far, most of panel display screen is LCDs (LCD, liquid crystal display), but It is always actively hardy to develop more economy, performance more superior in worldwide, while has with LCDs Differentiated novel flat-plate display screen.Recently as panel display screen of future generation by the organic electroluminescence device attracted attention, Compared with LCDs, there is low self-luminous, wide viewing angle, driving voltage, fast response time, that Flexible Displays lamp etc. can be achieved is all More advantages.Since invention the 1980s, organic electroluminescence device has industrially been applied, for example is used for Camera, computer, mobile phone, TV play display etc., due to all circles' lasting input for many years and unremitting effort, organic electroluminescence hair Light technology has had great development.Nevertheless, the problems such as short life, efficiency is low still govern organic electroluminescent The development of device.
Organic electroluminescence device receives the hole injection layer in hole, for transporting holes by substrate, anode, from anode Electron-blocking layer, hole and the electronics that hole transmission layer, prevention electron emitting layer enter hole transmission layer are combined and lighted Luminescent layer, tissue hole from luminescent layer enter electron transfer layer hole blocking layer, from negative electrode receive electronics electronics note Enter layer and negative electrode is formed.
The driving principle of organic electroluminescence device is as follows：To between above-mentioned anode and negative electrode apply voltage when, from anode Injected holes will be moved to luminescent layer via hole injection layer and hole transmission layer.Meanwhile electronics from negative electrode via electronics Implanted layer and electron transfer layer, are injected into luminescent layer, in luminescent layer with carrier in conjunction with and form exciton.Exciton is in this shape Become under state and turn to ground state, thus, the fluorescence mulecular luminescence of luminescent layer, form portrait.Now, excitation state passes through singlet excited Ground state is returned to, the light issued is called " fluorescence "；Ground state is returned to by triplet excited state, the light issued is called " phosphorus Light ".It is 25% to return to base probability of state by singlet excited, and it is 75% to return to base probability of state by triplet excited state, because This, luminous efficiency is limited；If using phosphorescence, triplet 75% and singlet excited 25% may serve to light, therefore, reason For upper, internal quantum can reach 100%.The problem of this organic electroluminescence device maximum is that service life is short Low with luminous efficiency, with the large area of display screen, service life is short low with luminous efficiency as the part for having to solution.
Efficiency and life-span, driving voltage etc. are interrelated, and when efficiency improves, relatively driving voltage declines, with drive The decline of dynamic voltage, reduce by the crystallization of organic substance caused by the Joule heating occurred when driving, as a result show Go out the tendency of life.But merely improving above-mentioned organic matter layer can not make its efficiency maximize.This is because, when each During the combination of the formation such as energy level and T1 values, the inherent characteristic of material (mobility, interfacial characteristics etc.) between organic matter layer optimization, Long-life and high efficiency can not be realized simultaneously.
As the hole transmission layer substance migration aromatic amine in organic electroluminescence device, this is because, in general, Under a variety of prior arts, in terms of the performance of lifting organic electroluminescence device, the effectiveness of the amine of plurality of classes is disclosed.It is right For the hole transporting material factor, the part to get a promotion includes higher hole transport motility, more unsetting knot Structure, higher glass transition temperature, better electron chemistry stability.It is made using the amine that this each side gets a promotion Organic electroluminescence device, performance in every respect is also improved, as luminous efficiency is higher, operating and storage life more Length, heat resistance are more excellent.For example, in the performance in terms of Van also waits the U.S. Patent No. 5061569 of trading transfer, it is open Improved arylamine hole transporting material.In the U.S. Patent No. 5554450 of the trading transfer such as Shi, disclose by A series of aromatic amines of high glass transition temperature that high temperature organic electroluminescence device designs, possessing 165 one-tenth or so. In Shirota etc. U.S. Patent No. 5374489, disclose to form stable amorphous glass, and as outstanding hole The m-MTDATA as new pi-conjugated star numerator that transport materials work.
In hole transmission layer in organic electroluminescence device, typically have without using other in addition to aromatic amine Machine compound, aromatic amine have the characteristic of hole transport by common cognition.But as double-deck organic electroluminescence device When interior hole transmission layer uses aromatic amine, the shortcomings that important be present.Because amine generally falls into very strong electron donor, they with The luminescent substance interaction used in electron transfer layer, forms fluorescence quenching center, so as to reduce organic electroluminescence device Luminous efficiency.
In addition, in organic electroluminescence device, in order to solve the luminous problem in hole transmission layer, it is necessary to passed in hole Luminous auxiliary layer is set between defeated layer and luminescent layer, needs to develop according to the mutually different of respective luminescent layer (R, G, B) at present Luminous auxiliary layer.In general, electronics is communicated to luminescent layer from electron transfer layer, and hole is communicated to luminous from hole transmission layer Layer, both form exciton by recombinant.But the material used in hole transmission layer must have relatively low HOMO values, Therefore, relatively low T1 values are largely possessed, thus, the exciton generated in luminescent layer flow to hole transmission layer, as a result causes Charge unbalance in luminescent layer, lighted in hole transmission layer or in hole transport bed boundary, produce organic electroluminescence The phenomenon that the excitation of part is low, efficiency and life-span decline.In addition, faster material can be used to reduce driving in hole mobility Voltage, still, because hole mobility is faster than electron mobility, therefore, cause charge unbalance in luminescent layer, so as to can also lead The problem of excitation and efficiency that cause organic electroluminescence device occur are low, lifetime.
On the other hand, it is necessary to develop the hole injection layer material for possessing high glass transition temperature, i.e. delay metallic compound Solve one of the reason for organic electro-luminescence device lifetime shortening from anode electrode (ITO) to organic layer diffusion, and it is right The Joule heating occurred when device drive has sufficiently stable characteristic.The glass transition temperature of hole transport layer material compared with Low, in driving element, having makes the characteristic that the uniformity of film surface declines, and report display, this problem is to device lifetime Have a huge impact.In addition, organic electroluminescence device is mainly formed by the method for deposition, need to develop electricity at present There is the material of durability, i.e. need to develop heat resistance strong material during plating.In order to give full play to organic electroluminescence device Excellent characteristic as described above, the material of organic matter layer, such as hole injecting material, hole transport thing are formed in device Matter, luminescent substance, electric transmission thing, electron injection material etc. must be stable and efficient materials, but not open fully also at present Send the organic material of stable and efficient organic electroluminescence device.Therefore, the art requires to develop always have Low voltage drive, high efficiency, the new material of long-life.
The content of the invention
The technical problem of solution：The purpose of the present invention is overcome the deficiencies in the prior art and provides a kind of organic electroluminescent Compound, the organic compound can be used as hole injection layer material, hole transport layer material, emitting layer material, electronics barrier Layer material and covering layer material, for that can reduce driving voltage in organic electroluminescence device, improve luminous efficiency, brightness, Heat endurance, color purity and device lifetime.
Technical scheme：A kind of organic electroluminescent compounds, structural formula is as shown in formula I：
In above formula, R1、R4For substituted or unsubstituted phenyl, xenyl, pyridine radicals, pyrimidine radicals or triazine radical, R2、R3For Substituted or unsubstituted phenyl, naphthyl, anthryl, phenanthryl or xenyl, R5、R6For substituted or unsubstituted phenyl, R7、R8To take Generation or the heteroaryl that unsubstituted phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, carbazyl, spiro fluorene or nuclear atom number are 5~20；Y1、 Y2、Y3For singly-bound ,-CH3Or-CH2CH3, it is-CH3Or-CH2CH3When, a, b, c are 0 or 1, and meet 1≤a+b+c≤3；Y5、Y6、 Y7For singly-bound ,-CH3Or-CH2CH3, it is-CH3Or-CH2CH3When, d, e, f are 0 or 1, and meet 1≤d+e+f≤3.
Further, R1、R4Phenyl, xenyl, pyridine radicals, in pyrimidine radicals and triazine radical, one or more hydrogen By C1~C10 straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF3Or Si (CH3)3Substitution.
Further, R2、R3Phenyl, naphthyl, anthryl, in phenanthryl and xenyl, one or more hydrogen by C1~ C10 straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
Further, R5、R6Phenyl in, one or more hydrogen is by C1~C10 straight or branched alkyl, C3 ~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
Further, R7、R8Phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, carbazyl, spiro fluorene or nuclear atom number be 5~20 Heteroaryl in, the hydrogen of one and the above is by hydrogen, C1~C10 straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 Alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
Further, the compound of formula I is any one in following compounds：
A kind of organic electroluminescence device of the organic electroluminescent compounds comprising described in claim 1.
Beneficial effect：Compound provided by the invention can be used as hole injection layer material, hole transport layer material, light Layer material, electron-blocking layer material and covering layer material, reduction driving voltage is played, improve efficiency, efficiency, brightness, thermostabilization Property, excitation, life-span and other effects.In addition, the organic electroluminescence device manufactured using this organic compound have high efficiency and The excellent properties of long-life.
Embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.Without departing substantially from In the case of spirit and essence of the invention, the modification and replacement made to the inventive method, step or condition, the present invention is belonged to Scope.Unless otherwise specified, the conventional meanses that technological means used in embodiment is well known to those skilled in the art.
A kind of organic electroluminescent compounds, structural formula is as shown in formula I：
In above formula, R1、R4For substituted or unsubstituted phenyl, xenyl, pyridine radicals, pyrimidine radicals or triazine radical, R2、R3For Substituted or unsubstituted phenyl, naphthyl, anthryl, phenanthryl or xenyl, R5、R6For substituted or unsubstituted phenyl, R7、R8To take Generation or the heteroaryl that unsubstituted phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, carbazyl, spiro fluorene or nuclear atom number are 5~20；Y1、 Y2、Y3For singly-bound ,-CH3Or-CH2CH3, it is-CH3Or-CH2CH3When, a, b, c are 0 or 1, and meet 1≤a+b+c≤3；Y5、Y6、 Y7For singly-bound ,-CH3Or-CH2CH3, it is-CH3Or-CH2CH3When, d, e, f are 0 or 1, and meet 1≤d+e+f≤3.
R1、R4Phenyl, xenyl, pyridine radicals, in pyrimidine radicals and triazine radical, one or more hydrogen is by C1~C10 Straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF3Or Si (CH3)3Substitution.
R2、R3Phenyl, naphthyl, anthryl, in phenanthryl and xenyl, one or more hydrogen is by C1~C10 straight chain Or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
R5、R6Phenyl in, one or more hydrogen is by C1~C10 straight or branched alkyl, C3~C12 ring Alkyl, C1~C10 alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
R7、R8Phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, carbazyl, spiro fluorene or nuclear atom number be 5~20 heteroaryl In, the hydrogen of one and the above by hydrogen, C1~C10 straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alcoxyl Base, halogen, CN, CF3And Si (CH3)3Substitution.
The compound can be used as hole injection layer material, hole transport layer material, emitting layer material, electron-blocking layer material Material and CPL materials are used for organic electroluminescence device material.By taking emitting layer material as an example, green phosphorescent or red main body can be used as Material.In addition, hole injection layer, hole transmission layer, luminescent layer, electron-blocking layer and CPL formation, its material exist for convenience The various forms of needs, such as liquid can not only be made during preparation, conventional material can also be added.
Present invention also offers a kind of organic electroluminescence device for including the organic electroluminescent compounds.The Organic Electricity Electroluminescence device has presses anode (hole injecting electrode), hole injection layer (HIL), hole transmission layer (HTL), luminescent layer successively (EML) construction that electron transfer layer (ETL), electron injecting layer (EIL) and negative electrode (electron injection electrode) are sequentially accumulated, it is possible Words, electron-blocking layer (EBL) can also be added between anode and luminescent layer, hole barrier is added between negative electrode and luminescent layer Layer (HBL), and in cathode surface addition coating (CPL).
The manufacture method of the organic electroluminescence device, comprises the following steps：
Step 1, anode material is crossed by modeling using conventional method and forms anode, used substrate selection tool in substrate surface There are the glass substrate or transparent plastic substrate of good transparency, surface smoothness, operability and water proofing property, anode material can make With transparent and superior conductibility ITO, IZO, SnO2, ZnO etc..
Step 2, anode surface by hole injection layer material (HIL) vacuum heat deposition or is spin-coated on using conventional method, it is empty Organic compound of the layer material except the present invention is injected in cave, can also be CuPc, m-MTDATA, m-MTDAPB, star-like amine TCTA, 2-TNATA or the IDE406 that can be bought from Japanese Idemitsu Kosen Co., Ltd. etc..
Step 3, hole injection layer table by hole transport layer material (HTL) vacuum heat deposition or is spin-coated on using conventional method Face forms hole transmission layer.Hole transport layer material can also be α-NPD, NPB or TPD except the organic compound of the present invention.
Step 4, hole transport layer surface by emitting layer material (EML) vacuum heat deposition or is spin-coated on using conventional method, Form luminescent layer.Used emitting layer material, when independent luminescent substance or light emitting host material is green, this hair can be used Bright organic compound, or three (8-hydroxyquinoline) aluminium (Alq3)；For blueness when, can use Balq, DPVBi series, loop coil Material, loop coil-DPVBi, LiPBO, double (distyrene) benzene, aluminium-quinoline metal complex, imidazoles, the metal of thiazole or oxazole Complex compound etc..
The present invention organic compound be also used as phosphorescent red main substance use, in emitting layer material also have with The doping (dopant) that light emitting host is used together, fluorescence doping can use Japanese Idemitsu Kosen Co., Ltd. IDE102, IDE105；Phosphorescence doping can use Ir (ppy) 3, FIrpic (bibliography [Chihaya Adachi et al., Appl.Phys.Lett., 2001,79,3082-3084]), PtOEP, TBE002 (Cobion companies) etc..
Step 5, luminous layer surface shape by electron transport layer materials (ETL) vacuum heat deposition or is spin-coated on using conventional method Into electron transfer layer.There is no particular limitation for electron transport layer materials, preferably using Alq3.
Step 6, electron transfer layer table by electron injecting layer material (EIL) vacuum heat deposition or is spin-coated on using conventional method Face, form electron injecting layer.Electron injecting layer material can be LiF, Liq, Li2O, BaO, NaCl, CsF etc..
Step 7, electron injecting layer by cathode material vacuum heat deposition or is spin-coated on using conventional method, forms negative electrode.It is cloudy Pole material, can be Li, Al, Al-Li, Ca, Mg, Mg-In, Mg-Ag etc..Alternatively, it is also possible to use tin indium oxide (ITO) or oxygen Change indium zinc (IZO) and light transmissive transparent cathode is made.
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.Using normal Rule method is by hole blocking layer material (HBL) vacuum heat deposition or is spin-coated on luminous layer surface, forms hole blocking layer.Hole hinders There is no particular limitation for interlayer material, preferably organic compound of the invention, Liq, 2- methyl -8-hydroxyquinoline parazon Close aluminium, BCP and LiF etc..
Further, coating (CPL) can also be further formed in cathode surface, covering layer material can select this hair Bright organic compound.
Embodiment 1
The synthesis of compound (6)
The synthesis of intermediate A
【Reaction equation 1】
31.6g N- phenyl carbazole -3- boric acid and 28.3g are added in 1L three-necked flask to bromo-iodobenzene, lead to nitrogen 15 Minute, 450mL toluene and the dissolving of 10mL ethanol are added, adds 150mL K2CO3The aqueous solution of (3.0eq., 2M), is eventually adding 2.3g Pd(PPh3)4(2mol).110 DEG C are warming up to, reaction terminates for 5 hours.Add charcoal absorption, filter, rotation removes solvent, does It is dry, with toluene and ethyl alcohol recrystallization, obtain 33g intermediate As (yield 83%).
The synthesis of intermediate B
【Reaction equation 2】
37.2g 2- iodobenzenes boric acid and 3- aminobphenyl 28g are added in dry 2L three-necked flasks, adds and dries simultaneously The 600mL toluene of degasification makees solvent.Add 43.2g sodium tert-butoxides, 0.7g catalyst acetic acids palladium (2%mol) and 3.7g parts The double diphenyl phosphines (BINAP, 4%mol) of 1,1'- dinaphthalene -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, is added Charcoal absorption, filter, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 38.2g intermediate Bs (yield 88%).
Intermediate C synthesis
【Reaction equation 3】
The bromo- 9,9 '-dimethyl fluorenes of product Intermediate B and 32.8g 3- that 38.2g reaction equations 2 obtain are added to the three of 1L In mouthful flask, add 450mL toluene and the dissolving of 10mL ethanol, lead to nitrogen 15 minutes, add 180mL K2CO3 (3.0eq., Aqueous solution 2M), it is eventually adding 2.8g Pd (PPh3) 4 (2mol%).110 DEG C are warming up to, reaction terminates for 5 hours.Add activated carbon Absorption, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 37.8g intermediates C (yield 72%).
The synthesis of compound (6)
【Reaction equation 4】
Product Intermediate A and the 37.8g reaction equation 3 that 31.1g is obtained by reaction equation 1 is added in dry 2L three-necked flasks Obtained product Intermediate C, add dry and degasification 600mL toluene and make solvent.Add 22.6g sodium tert-butoxides, 0.4g Catalyst acetic acid palladium (2%mol) and 2.0g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.It is warming up to 110 DEG C, reaction terminates overnight.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 38.4g products (yield 65%).
1H NMR(DMSO,300Hz):300Hz):δ (ppm)=8.20-8.10 (s, 1H), 8.10-7.80 (d, 3H), 7.75-6.90(m,21H),6.89-6.54(m,9H),1.35(s,6H)
MS(FAB):752(M+)
Embodiment 2
The synthesis of compound (14)
Intermediate D synthesis
【Reaction equation 5】
31.6g N- phenyl carbazole -3- boric acid and 28.3g are added in 1L three-necked flask to bromo-iodobenzene, lead to nitrogen 15 Minute, 450mL toluene and the dissolving of 10mL ethanol are added, adds 150mL K2CO3The aqueous solution of (3.0eq., 2M), is eventually adding 2.3g Pd(PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 5 hours.Add charcoal absorption, filter, rotation removes solvent, does It is dry, with toluene and ethyl alcohol recrystallization, obtain 33g intermediates D (yield 83%).
The synthesis of intermediate E
【Reaction equation 6】
27.3g 2- bromo- 9,9 '-dimethyl fluorene and 4- aminobphenyl 18.6g are added in dry 2L three-necked flasks, then Add dry and degasification 600mL toluene and make solvent.Add 28.8g sodium tert-butoxides, 0.45g catalyst acetic acids palladium (2%mol) With 2.5g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Cooling To room temperature, add charcoal absorption, filter, rotation removes solvent, and with toluene and ethyl alcohol recrystallization, obtaining 33g intermediate Es, (yield is 91%).
The synthesis of compound (14)
【Reaction equation 7】
Add what product Intermediate D and the 33g reaction equation 6 that 33g reaction equations 5 obtain obtained in dry 2L three-necked flasks Product Intermediate E, add dry and degasification 600mL toluene and make solvent.Add 24g sodium tert-butoxides, 0.4g catalyst vinegar Sour palladium (2%mol) and 2.1g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction Terminate overnight.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 35g products (yield 62%).
1H NMR(DMSO,300Hz):δ (ppm)=8.20-8.10 (s, 2H), 8.10-7.80 (d, 4H), 7.75-6.91 (m,20H),6.90-6.55(m,4H),1.35(s,6H)
MS(FAB):677(M+)
Embodiment 3
The synthesis of compound (21)
Intermediate F synthesis
【Reaction equation 8】
By the bromo- 9- of 64.97g 2- (the bromo- 4- methoxybenzenes of 2-) -9H- carbazoles, [1,3- is double for the chlorination of 1.7g catalyst pi-allyls (2,6- diisopropyl benzenes) imidazoles -2- bases] palladium (NHC) Pd (allyl) Cl (2mol%) and 62.2g K2CO3 (3.00eq.) exist Under conditions of logical nitrogen, it is dissolved into the 1000ml DMAs (DMA) of degasification and is warming up to 130 DEG C.Question response knot Beam, reaction solution is poured into water, extracted with dichloromethane, organic phase is dried, and dress silica gel crosses post, obtains 43.4g (yields 82.2%).
Intermediate G synthesis
【Reaction equation 9】
Bromobenzeneboronic acid between product Intermediate F and 27.2g that 43.4g reaction equations 8 obtain is added in 2L three-necked flask, 800mL toluene and the dissolving of 200mL ethanol are added, leads to nitrogen 15 minutes, adds 185mL K2CO3(3.0eq., 2M's) is water-soluble Liquid, it is eventually adding 2.8g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, adds activated carbon Absorption, filter, rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 44.9g intermediates G (yield 85%).
The synthesis of compound (21)
【Reaction equation 10】
The product Intermediate G and N- phenyl -9,9- two that 44.9g reaction equations 9 obtain is added in dry 2L three-necked flasks Methyl fluorenes -2- amine 32.9g, add dry and degasification 900mL toluene and make solvent.30.2g sodium tert-butoxides are added, 0.5g is urged Agent palladium (2%mol) and 2.6g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.It is warming up to 110 DEG C, reaction terminates overnight.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 45.1g products (yield 66%).
1H NMR(DMSO,300Hz):δ (ppm)=8.20-8.10 (d, 1H), 8.10-7.80 (d, 4H), 7.75-6.91 (m,17H),6.90-6.55(m,3H),3.91-3.52(s,3H),1.35(s,6H)
MS(FAB):630(M+)
Embodiment 4
The synthesis of compound (29)
Intermediate H synthesis
【Reaction equation 11】
25.7g 1- bromines anthracenes and 27.3g 4- bromophenyl aniline are added in dry 1L three-necked flasks, adds and dries simultaneously The 500mL toluene of degasification makees solvent.Add 28.8g sodium tert-butoxides, 0.45g catalyst acetic acids palladium (2%mol) and 2.5g parts The double diphenyl phosphines (BINAP, 4%mol) of 1,1'- dinaphthalene -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, is added Charcoal absorption, filter, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 36.5g intermediates H (yield 86%).
The synthesis of compound (29)
【Reaction equation 12】
Halides intermediate H and the 27.2g boric acid that 36.5g reaction equations 11 obtain is added in 2L three-necked flask, added Enter 800mL toluene and the dissolving of 200mL ethanol, lead to nitrogen 15 minutes, add 130mL K2CO3The aqueous solution of (3.0eq., 2M), It is eventually adding 2.0g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, filter, rotation removes Solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 30.8g products (yield 61%).
1H NMR(DMSO,300Hz):δ (ppm)=8.50-8.25 (s, 2H), 8.20-8.10 (s, H), 8.10-7.80 (d,4H),7.75-6.91(m,9H),6.90-6.55(m,8H),1.35(s,6H)
MS(FAB):586(M+)
Embodiment 5
The synthesis of compound (39)
The synthesis of intermediate compound I
【Reaction equation 13】
Bromo-iodobenzene and 27.5g carbazoles between 42.3g are added in dry 2L three-necked flasks, adds and dries and degasification 800mL toluene makees solvent.43.2g sodium tert-butoxides (3eq.), 0.67g catalyst acetic acids palladium (2%mol) and 3.7g ligand 1s are added, The double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, adds work Property charcoal absorption, filter, rotation remove solvent, with toluene and ethyl alcohol recrystallization, obtain 40.9g intermediate compound Is (yield 90%).
Intermediate J synthesis
【Reaction equation 14】
Experimental provision is fully dried, the product Intermediate I that 40.9g reaction equations 13 obtain is added in 2L three-necked flasks, The dried tetrahydrofurans of 800mL are added, -78 DEG C are cooled to after dissolving, 56mL 2.5M n-BuLi is added dropwise.After completion of dropwise addition Stir 1 hour at such a temperature, then 17g (1.3eq.) trimethylborate is added dropwise at such a temperature, be stirred at room temperature after completion of dropwise addition Overnight.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 i.e. intermediate J, and 26.2g (is produced 72%) rate is.
Intermediate K synthesis
【Reaction equation 15】
The Bromopyrimidines of 35.7g 4.6- bis- and 27.9g 3- aminobphenyls are added in dry 2L three-necked flasks, is added dry Dry and degasification 800mL toluene makees solvent.Add 43.2g sodium tert-butoxides, 0.67g catalyst acetic acids palladium (2%mol) and 3.7g Ligand 1, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight.It is cooled to room Temperature, add charcoal absorption, filter, rotation removes solvent, and with toluene and ethyl alcohol recrystallization, obtaining 33.3g intermediates K, (yield is 68%).
Intermediate L synthesis
【Reaction equation 16】
During the bromo- fluorenes of 9,9 '-spiral shell two of addition 36.7g 2- and 33.3g reaction equations 15 obtain in dry 2L three-necked flasks Mesosome K, add dry and degasification 800mL toluene and make solvent.Add 26.8g sodium tert-butoxides, 0.42g catalyst acetic acid palladiums (2%mol) and 2.3g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction is overnight Terminate.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 44g intermediates L (yield 74%).
The synthesis of compound (39)
【Reaction equation 17】
The boric acid that the halides and 21.7g reaction equations 14 that 44g reaction equations 16 are obtained obtain is added to 2L three-necked flask In, 900mL toluene and the dissolving of 220mL ethanol are added, leads to nitrogen 15 minutes, adds 100mL K2CO3The water of (3.0eq., 2M) Solution, it is eventually adding 1.6g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, take out Filter, rotation remove solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 32g products (yield 58%).
1H NMR(DMSO,300Hz):):δ (ppm)=8.55-8.40 (d, 1H), 8.38-8.22 (s, 2H), 8.20- 8.10(d,1H),8.10-7.80(m,4H),7.75-6.90(m,26H),6.88-6.54(m,4H)
MS(FAB):802(M+)
Embodiment 6
The synthesis of organic matter (51)
Intermediate M synthesis
【Reaction equation 18】
31.6g 2- bromopyridines and 34.4g 3- bromanilines are added in dry 2L three-necked flasks, is added and is dried and remove The 600mL toluene that gas is crossed makees solvent.57.7g sodium tert-butoxides, 0.9g catalyst acetic acids palladium (2%mol) and 5.0g ligand 1s are added, The double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, adds work Property charcoal absorption, filter, rotation remove solvent, with toluene and ethyl alcohol recrystallization, obtain 45.3g intermediates M (yield 91%).
Intermediate N synthesis
【Reaction equation 19】
It is luxuriant and rich with fragrance that the product Intermediate M and 42.5g 9- bromines that 45.3g reaction equations 18 obtain are added in dry 2L three-necked flasks, Add dry and degasification 900mL toluene and make solvent.Add 47.7g sodium tert-butoxides, 0.74g catalyst acetic acids palladium (2% Mol) and 4.1g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight. Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 51.3g intermediates N (productions 73%) rate is.
Intermediate O synthesis
【Reaction equation 20】
Bromo-derivative 51.3g and 26.8g the 5- bromopyridine -3- boric acid that reaction equation 19 obtains is added to 2L three-necked flask In, 1000mL toluene and the dissolving of 250mL ethanol are added, leads to nitrogen 15 minutes, adds 180mL K2CO3The water of (3.0eq., 2M) Solution, it is eventually adding 2.8g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, take out Filter, rotation remove solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 50.3g intermediates O (yield 83%).
Intermediate P synthesis
【Reaction equation 21】
The bromo- 9H- carbazoles of 49.2g 1- are dissolved into 1000mL DMF, add 28.7g cuprous cyanides (CuCN), heating To 150 DEG C, 18h is reacted.Question response terminates, and with suction filtered through kieselguhr, adds water and dichloromethane to extract, washing three times, is dried, and rotation removes Solvent, with toluene and ethyl alcohol recrystallization, obtain 33.8g intermediates P (yield 88%).
The synthesis of compound (51)
【Reaction equation 22】
The bromo-derivative and 21.2g reaction equations 21 that addition 50.3g reaction equations 20 obtain in dry 2L three-necked flasks obtain Product, add and dry and the 1000mL toluene of degasification makees solvent.Add 28.9g sodium tert-butoxides, 0.45g catalyst acetic acids Palladium (2%mol) and 2.5g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, was reacted Night terminates.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 39.9g products (yield 65%).
1H NMR(DMSO,300Hz):δ (ppm)=8.90-8.62 (s, 1H), 8.60-8.43 (d, 2H), 8.40-8.21 (s,1H),8.20-8.10(d,2H),8.10-7.80(d,2H),7.75-6.91(m,17H),6.87-6.52(m,2H)
MS(FAB):613(M+)
Embodiment 7
The synthesis of compound (62)
Intermediate Q synthesis
【Reaction equation 23】
31.4g bromobenzenes and the bromo- 9H- carbazoles of 54.1g4- are added in dry 2L three-necked flasks, adds and dries simultaneously degasification The 600mL toluene crossed makees solvent.Add 57.7g sodium tert-butoxides, 0.9g catalyst acetic acids palladium (2%mol) and 5.0g ligand 1s, 1'- The double diphenyl phosphines (BINAP, 4%mol) of dinaphthalene -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, adds activated carbon Absorption, filter, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 52.8g intermediates Q (yield 82%).
Intermediate R synthesis
【Reaction equation 24】
Experimental provision is fully dried, the product Intermediate Q that 52.8g reaction equations 23 obtain is added in 2L three-necked flasks, The dried tetrahydrofurans of 1000mL are added, -78 DEG C are cooled to after dissolving, 72mL 2.5M n-BuLi is added dropwise.After completion of dropwise addition Stir 1 hour at such a temperature, then 21.9g (1.3eq.) trimethylborate is added dropwise at such a temperature, room temperature is stirred after completion of dropwise addition Mix overnight.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 i.e. intermediate R, and 33.9g (is produced 72%) rate is.
Intermediate S synthesis
【Reaction equation 25】
25.7g 2- bromines anthracenes and 10.2g aniline are added in dry 1L three-necked flasks, is added dry and degasification 500mL toluene makees solvent.Add 28.8g sodium tert-butoxides, 0.45g catalyst acetic acids palladium (2%mol) and 2.5g ligand 1s, 1'- connection The double diphenyl phosphines (BINAP, 4%mol) of naphthalene -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, adds activated carbon to inhale It is attached, filter, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 23.7g intermediates S (yield 88%).
Intermediate T synthesis
【Reaction equation 26】
Bis- bromo- [1,3,5] triazines of 19.1g 2,4- are added in dry 1L three-necked flasks and 23.7g reaction equations 25 obtain Intermediate S, add and dry and the 400mL toluene of degasification makees solvent.Add 23.1g sodium tert-butoxides, 0.36g catalyst vinegar Sour palladium (2%mol) and 2.0g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction Terminate overnight.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains among 26g Body T (yield 76%).
The synthesis of compound (62)
【Reaction equation 27】
The product that halides 26g and the 19.2g reaction equation 24 that reaction equation 26 obtains obtains is added to 2L three-necked flask In, 500mL toluene and the dissolving of 125mL ethanol are added, leads to nitrogen 15 minutes, adds 90mL K2CO3(3.0eq., 2M's) is water-soluble Liquid, it is eventually adding 1.4g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, filter, Rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 24g products (yield 67%).
1H NMR(DMSO,300Hz):δ (ppm)=9.10-8.82 (s, 1H), 8.50-8.25 (d, 1H), 8.23-8.11 (s,2H),8.10-7.80(d,4H),7.75-6.88(m,17H),6.86-6.53(m,2H)
MS(FAB):589(M+)
Embodiment 8
The synthesis of compound (90)
Intermediate U synthesis
【Reaction equation 28】
25.7g 2- bromines anthracenes and 27.1g are added in dry 1L three-necked flasks to bromo-iodobenzene, adds and dries simultaneously degasification The 300mL toluene crossed makees solvent.28.8g sodium tert-butoxides, 0.45g catalyst acetic acids palladium (2%mol) and 2.5g ligand 1s are added, The double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, adds work Property charcoal absorption, filter, rotation remove solvent, with toluene and ethyl alcohol recrystallization, obtain 36.3g intermediates U (yield 86%).
Intermediate V synthesis
【Reaction equation 29】
The product 36.3g that reaction equation 28 obtains is added in 1L three-necked flask, it is molten to add 600mL dichloromethane Solution, 16.8g NBS (1.1eq.) are added, lucifuge is stirred overnight at room temperature.Increasing amount water after reaction terminates, there is solid precipitation, filters, Filter cake is washed with water three times, dries, with toluene and ethyl alcohol recrystallization, obtains 28g intermediates V (yield 65%).
Intermediate W synthesis
【Reaction equation 30】
Experimental provision is fully dried, 27.3g halides are added in 2L three-necked flasks, adds 600mL dried four Hydrogen furans, -78 DEG C are cooled to after dissolving, 44mL 2.5M n-BuLi is added dropwise.Stirred at such a temperature after completion of dropwise addition 1 hour, 13.4g (1.3eq.) trimethylborate is added dropwise at such a temperature again, is stirred overnight at room temperature after completion of dropwise addition.Question response terminates, and adds Enter 4M hydrochloric acid solutions, extracted with dichloromethane, organic phase is washed to neutrality with saturated common salt, dries, and rotation removes solvent, with acetic acid second Ester boils obtained crude product, and filtering, filter cake is boric acid product i.e. intermediate W, 19g (yield 80%).
The synthesis of intermediate X
【Reaction equation 31】
The boric acid that the halides and 14.6g reaction equations 30 that 28g reaction equations 29 are obtained obtain is added to 2L three-necked flask In, 800mL toluene and the dissolving of 200mL ethanol are added, leads to nitrogen 15 minutes, adds 84mL K2CO3(3.0eq., 2M's) is water-soluble Liquid, it is eventually adding 1.3g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, filter, Rotation removes solvent, dries, with toluene and ethyl alcohol recrystallization, obtains 24.7g intermediate Xs (yield 72%).
Intermediate Y synthesis
【Reaction equation 32】
35.4g halides, the chlorination of 1.1g catalyst pi-allyls [1,3- double (2,6- diisopropyl benzene) imidazoles -2- bases] palladium (NHC) Pd (allyl) Cl (2mol%) and 41.5g K2CO3(3.00eq.) is dissolved into degasification under conditions of logical nitrogen 130 DEG C are warming up in 700mL DMAC N,N' dimethyl acetamides (DMA).Question response terminates, and reaction solution is poured into water, and uses dichloromethane Alkane is extracted, and organic phase is dried, and dress silica gel crosses post, obtains 19.1g intermediates Y (yield 70%).
Intermediate Z synthesis
【Reaction equation 33】
The product 19.1g that reaction equation 32 obtains is added in 1L three-necked flask, it is molten to add 400mL dichloromethane Solution, 13.7g NBS (1.1eq.) are added, lucifuge is stirred overnight at room temperature.Increasing amount water after reaction terminates, there is solid precipitation, filters, Filter cake is washed with water three times, dries, with toluene and ethyl alcohol recrystallization, obtains 19.9g intermediates Z (yield 81%).
The synthesis of intermediate I
【Reaction equation 34】
Experimental provision is fully dried, the halides that 19.9g reaction equations 33 obtain are added in 2L three-necked flasks, are added Tetrahydrofuran dried 400mL, -78 DEG C are cooled to after dissolving, 25mL 2.5M n-BuLi is added dropwise.At this after completion of dropwise addition At a temperature of stir 1 hour, then at such a temperature be added dropwise 6.4g (1.3eq.) trimethylborate, room temperature is stirred after completion of dropwise addition Night.Question response terminates, and adds 4M hydrochloric acid solutions, is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, dries, Rotation remove solvent, boils obtained crude product with ethyl acetate, filters, and filter cake is boric acid product Intermediate I, and (yield is 15.2g 85%).
The synthesis of compound (90)
【Reaction equation 35】
The boric acid that the halides and 14.g reaction equations 34 that 24.7g reaction equations 31 are obtained obtain is added to 2L three-necked flask In, 500mL toluene and the dissolving of 1250mL ethanol are added, leads to nitrogen 15 minutes, adds 60mL K2CO3The water of (3.0eq., 2M) Solution, it is eventually adding 0.93g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, take out Filter, rotation remove solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 23.7g products (yield 73%).
1H NMR(DMSO,300Hz):δ (ppm)=8.80-8.20 (d, 6H), 8.18-7.80 (d, 4H), 7.75-6.91 (m,18H),6.89-6.54(m,3H),3.93-3.51(s,3H),1.35(s,6H)
MS(FAB):804(M+)
Embodiment 9
The synthesis of compound (112)
The synthesis of intermediate II
【Reaction equation 36】
23.8g 2 is added in dry 1L three-necked flasks, the Bromopyrimidines of 4- bis- and 18.8g add drying to bromo-iodobenzene And the 300mL toluene of degasification makees solvent.28.8g sodium tert-butoxides are added, 0.45g catalyst acetic acids palladium (2%mol) and 2.5g match somebody with somebody Body 1, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight.It is cooled to room temperature, Add charcoal absorption, filter, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 26.9g intermediate IIs (yield 82%).
The synthesis of intermediate III
【Reaction equation 37】
By 28.6g 2,7- dibromine naphthalenes and 24.4g 1- anthracene boric acid are added in 2L three-necked flask, lead to nitrogen 15 minutes, 600mL toluene and the dissolving of 150mL ethanol are added, adds 150mL K2CO3The aqueous solution of (3.0eq., 2M), is eventually adding 2.3g Pd(PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 5 hours.Add charcoal absorption, filter, rotation removes solvent, dries, and uses Toluene and ethyl alcohol recrystallization, obtain 31.1g intermediates III (yield 81%).
The synthesis of intermediate IV
【Reaction equation 38】
The product and 28.6g reaction equations 37 containing amine that 26.9g reaction equations 36 obtain are added in dry 2L three-necked flasks Obtained bromo-derivative, add dry and degasification 600mL toluene and make solvent.Add 21.5g sodium tert-butoxides, 0.33g catalysis Agent palladium (2%mol) and 1.9g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, Reaction terminates overnight.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 37.2g intermediates IV (yield 79%).
The synthesis of intermediate V
【Reaction equation 39】
By 18.4g 3,6- dibromos carbazoles and the bromo- 2- fluorobenzene of 25.4g 1,4- bis-, 500mL N, N '-dimethyl formamide adds Enter into dried 1L three-necked flask, be slow added into 97.7g cesium carbonates, be warming up to 180 DEG C, react 5 hours and tie Beam.It is cooled to room temperature and adds water, extracted with dichloromethane, washed 3 times, dried, rotation removes solvent, and loading crosses pillar, obtains 31.7g Intermediate V (yield 79%).
The synthesis of intermediate VI
【Reaction equation 40】
Product 31.7g, 0.9g catalyst pi-allyl chlorination [1,3- double (2,6- diisopropyl benzene) miaows that reaction equation 39 obtains Azoles -2- bases] palladium (NHC) Pd (allyl) Cl (2mol%) and 32.8g K2CO3(3.00eq.) dissolves under conditions of logical nitrogen 130 DEG C are warming up into the 600mL DMAC N,N' dimethyl acetamides (DMA) of degasification.Question response terminates, and reaction solution is poured into water, Extracted with dichloromethane, organic phase is dried, and dress silica gel crosses post, obtains the 17.5g of intermediate VI (yield 69%).
The synthesis of intermediate VII
【Reaction equation 41】
Experimental provision is fully dried, the product that 17.5g reaction equations 40 obtain is added in 2L three-necked flasks, is added Tetrahydrofuran dried 800mL, -78 DEG C are cooled to after dissolving, 24mL 2.5M n-BuLi is added dropwise.At this after completion of dropwise addition At a temperature of stir 1 hour, then at such a temperature be added dropwise 7.3g (1.3eq.) trimethylborate, room temperature is stirred after completion of dropwise addition Night.Question response terminates, and adds 4M hydrochloric acid solutions, is extracted with dichloromethane, and organic phase is washed to neutrality with saturated common salt, dries, Rotation remove solvent, boils obtained crude product with ethyl acetate, filters, and filter cake is boric acid product Intermediate VII, and (yield is 13.7g 88%).
The synthesis of compound (112)
【Reaction equation 42】
The boric acid that the bromo-derivative and 13.7g reaction equations 41 that 27.6g reaction equations 38 are obtained obtain is added to 2L three mouthfuls of burnings In bottle, lead to nitrogen 15 minutes, add 600mL toluene and the dissolving of 150mL ethanol, add 65mL K2CO3The water of (3.0eq., 2M) Solution, it is eventually adding 1.0g Pd (PPh3)4(2mol%).110 DEG C are warming up to, reaction terminates for 5 hours.Add charcoal absorption, take out Filter, rotation remove solvent, dry, with toluene and ethyl alcohol recrystallization, obtain 22.5g products (yield 65%).
1H NMR(DMSO,300Hz):δ (ppm)=9.10-8.82 (s, 1H), 8.50-8.25 (d, 2H), 8.20-8.10 (m,2H),8.10-7.80(m,4H),7.75-6.91(m,23H),6.85-6.31(m,2H)
MS(FAB):790(M+)
Embodiment 10
The synthesis of compound (120)
The synthesis of intermediate VIII
【Reaction equation 43】
28.3g is added in dry 2L three-necked flasks to bromo-iodobenzene and 18.4g carbazoles, is added dry and degasification 600mL toluene makees solvent.Add 28.8g sodium tert-butoxides, 0.45g catalyst acetic acids palladium (2%mol) and 2.5g ligand 1s, 1'- connection The double diphenyl phosphines (BINAP, 4%mol) of naphthalene -2,2'-.110 DEG C are warming up to, reaction terminates overnight.Room temperature is cooled to, adds activated carbon to inhale It is attached, filter, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 28g intermediates VIII (yield 87%).
The synthesis of intermediate Ⅸ
【Reaction equation 44】
Biphenylboronic acids are added in 2L three-necked flask between bromo-derivative and 19.2g that 28g is obtained reaction equation 43, are added 600mL toluene and the dissolving of 150mL ethanol, lead to nitrogen 15 minutes, add 130mL K2CO3The aqueous solution of (3.0eq., 2M), most 2.0g Pd (PPh are added afterwards3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, filter, rotation is except molten Agent, dry, with toluene and ethyl alcohol recrystallization, obtain 27.7g intermediates Ⅸ (yield is 80%).
The synthesis of intermediate Ⅹ
【Reaction equation 45】
Iodobenzene boric acid is added in 2L three-necked flask between bromo-derivative and 19.0g that 27.7g reaction equations 44 are obtained, is added 600mL toluene and the dissolving of 150mL ethanol, lead to nitrogen 15 minutes, add 104mL K2CO3The aqueous solution of (3.0eq., 2M), most 1.6g Pd (PPh are added afterwards3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, filter, rotation is except molten Agent, dry, with toluene and ethyl alcohol recrystallization, obtain 29.7g intermediates Ⅹ (yield 82%).
The synthesis of intermediate Ⅺ
【Reaction equation 46】
The iodo thing and 9.0g 5- aminoquinolines that 29.7g reaction equations 45 obtain are added in dry 1L three-necked flasks, then Add dry and degasification 600mL toluene and make solvent.Add 16.4g sodium tert-butoxides, 0.26g catalyst acetic acids palladium (2%mol) With 1.42g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction terminates overnight.It is cold But to room temperature, add charcoal absorption, filter, rotation removes solvent, and with toluene and ethyl alcohol recrystallization, obtaining 26g intermediates Ⅺ, (yield is 85%).
The synthesis of intermediate Ⅻ
【Reaction equation 47】
By 28.6g 1,6- dibromine naphthalenes and 31.6g N- aminocarbazole -3- boric acid are added in 2L three-necked flask, are added 600mL toluene and the dissolving of 150mL ethanol, lead to nitrogen 15 minutes, add 150mL K2CO3The aqueous solution of (3.0eq., 2M), most 2.3g Pd (PPh are added afterwards3)4(2mol%).110 DEG C are warming up to, reaction terminates overnight.Add charcoal absorption, filter, rotation is except molten Agent, dry, with toluene and ethyl alcohol recrystallization, obtain 35.4g intermediates Ⅻ (yield 79%).
The synthesis of compound (120)
【Reaction equation 48】
The bromine that the product and 19.7g reaction equations 47 that addition 26g reaction equations 46 obtain in dry 1L three-necked flasks obtain For thing, add dry and degasification 400mL toluene and make solvent.Add 12.7g sodium tert-butoxides, 0.2g catalyst acetic acid palladiums (2%mol) and 1.1g ligand 1s, the double diphenyl phosphines (BINAP, 4%mol) of 1'- dinaphthalenes -2,2'-.110 DEG C are warming up to, reaction is overnight Terminate.Room temperature is cooled to, adds charcoal absorption, is filtered, rotation removes solvent, with toluene and ethyl alcohol recrystallization, obtains 25.8g products (yield 65%).
1H NMR(DMSO,300Hz):δ (ppm)=8.60-8.25 (d, 3H), 8.20-8.10 (s, 2H), 8.10-7.80 (d,4H),7.75-6.91(m,32H),6.87-6.51(m,3H)
MS(FAB):905(M+)
The compound represented by chemical formula 1 can be developed by the method for above-mentioned reaction equation 1~48.
The manufacture of the organic electroluminescence device of embodiment 11
Using ITO as reflecting layer anode grid substrate material, and use N2Plasma or UV-Ozone are surface-treated to it. Above anode grid substrate, deposited to HIL layersThe HAT-CN of thickness.Above above-mentioned htl layer, selection above-claimed cpd 1, 6th, 14,16,21,29,39,51,62,71,83,90,103,112,120 vacuum evaporationForm hole transmission layer.Above-mentioned Vacuum evaporation TCTA is formed on hole transmission layerElectron-blocking layer, above-mentioned electron-blocking layer evaporation can form blue EML 9,10-Bis (2-naphthyl) anthraces (ADN) is used as luminescent layer, adulterate about 5% with dopant 2,5,8, 11- tetrabutyl perylenes are formedLuminescent layer.Above it by anthracene derivant and Liq with 1:1 ratio mixing evaporationThickness to electron transfer layer, be deposited on electron transfer layerLiq as electron injecting layer.Finally in the moon Pole is depositedThe silver of thickness.Seal containing UV curable adhesives absorbent material in addition, being used in cathode surface, have with protection Organic electroluminescence devices are not influenceed by the oxygen in air or moisture.
Comparative example 1：The manufacture of organic electroluminescent
Above-mentioned chemical formula 1 is as hole injection layer material, hole transport layer material, electron-blocking layer material, luminescent layer master Body material and CPL materials, except replacing the compound in the present invention to use a-NPD situation, other situations are all used with embodiment 1 Identical method manufactures organic electroluminescence device.
The evaluating characteristics of organic electroluminescence device
It is 10mA/cm in current density2Under conditions of, to the organic electroluminescence device 1~15 of above-described embodiment manufacture It is as a result as shown in the table and the organic electroluminescence device of comparative example manufacture carries out performance measurement.
As seen from the above table, organic electroluminescence device driving voltage using the compounds of this invention is low, luminous efficiency is high.

Claims (7)

  1. A kind of 1. organic electroluminescent compounds, it is characterised in that：Structural formula is as shown in formula I：
    In above formula, R1、R4For substituted or unsubstituted phenyl, xenyl, pyridine radicals, pyrimidine radicals or triazine radical, R2、R3For substitution or Unsubstituted phenyl, naphthyl, anthryl, phenanthryl or xenyl, R5、R6For substituted or unsubstituted phenyl, R7、R8For substitution or not Substituted phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, carbazyl, spiro fluorene or nuclear atom number is 5~20 heteroaryl；Y1、Y2、Y3For Singly-bound ,-CH3Or-CH2CH3, it is-CH3Or-CH2CH3When, a, b, c are 0 or 1, and meet 1≤a+b+c≤3；Y5、Y6、Y7For list Key ,-CH3Or-CH2CH3, it is-CH3Or-CH2CH3When, d, e, f are 0 or 1, and meet 1≤d+e+f≤3.
  2. 2. organic electroluminescent compounds according to claim 1, it is characterised in that：R1、R4Phenyl, xenyl, pyridine In base, pyrimidine radicals and triazine radical, one or more hydrogen is by C1~C10 straight or branched alkyl, C3~C12 cycloalkanes Base, C1~C10 alkoxy, halogen, CN, CF3Or Si (CH3)3Substitution.
  3. 3. organic electroluminescent compounds according to claim 1, it is characterised in that：R2、R3Phenyl, naphthyl, anthryl, In phenanthryl and xenyl, one or more hydrogen is by C1~C10 straight or branched alkyl, C3~C12 cycloalkyl, C1 ~C10 alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
  4. 4. organic electroluminescent compounds according to claim 1, it is characterised in that：R5、R6Phenyl in, one or one It is individual more than hydrogen by C1~C10 straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
  5. 5. organic electroluminescent compounds according to claim 1, it is characterised in that：R7、R8Phenyl, naphthyl, anthryl, Phenanthryl, fluorenyl, carbazyl, spiro fluorene or nuclear atom number be in 5~20 heteroaryl, and the hydrogen of one and the above is by hydrogen, C1~C10 Straight or branched alkyl, C3~C12 cycloalkyl, C1~C10 alkoxy, halogen, CN, CF3And Si (CH3)3Substitution.
  6. 6. organic electroluminescent compounds according to claim 1, it is characterised in that：The compound of formula I is following chemical combination Any one in thing：
  7. A kind of 7. organic electroluminescence device of the organic electroluminescent compounds comprising described in any one of claim 1 to 7.
CN201610635159.XA 2016-08-05 2016-08-05 Organic electroluminescent compounds and the organic electroluminescence device using the compound Pending CN107686484A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610635159.XA CN107686484A (en) 2016-08-05 2016-08-05 Organic electroluminescent compounds and the organic electroluminescence device using the compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610635159.XA CN107686484A (en) 2016-08-05 2016-08-05 Organic electroluminescent compounds and the organic electroluminescence device using the compound

Publications (1)

Publication Number Publication Date
CN107686484A true CN107686484A (en) 2018-02-13

Family

ID=61151611

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610635159.XA Pending CN107686484A (en) 2016-08-05 2016-08-05 Organic electroluminescent compounds and the organic electroluminescence device using the compound

Country Status (1)

Country Link
CN (1) CN107686484A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467556A (en) * 2018-11-16 2019-03-15 烟台九目化学制品有限公司 The preparation and its application on OLED luminescent device of a kind of benzindole diindyl and Acridine derivatives
CN110938063A (en) * 2018-09-21 2020-03-31 东进世美肯株式会社 Novel compound for capping layer and organic light emitting device including the same
WO2020159099A1 (en) * 2019-02-01 2020-08-06 주식회사 이엘엠 Organic electroluminescent composition and organic electroluminescent element comprising same
WO2020171381A3 (en) * 2019-02-18 2020-10-22 주식회사 이엘엠 Organic electroluminescent composition, and organic electroluminescent element comprising same
WO2021034017A1 (en) * 2019-08-16 2021-02-25 주식회사 엘지화학 Novel compound and organic light emitting device using same
WO2021145429A1 (en) * 2020-01-15 2021-07-22 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
CN113272307A (en) * 2019-08-16 2021-08-17 株式会社Lg化学 Novel compound and organic light emitting device using the same
WO2023022417A1 (en) * 2021-08-20 2023-02-23 주식회사 랩토 Cyano group-substituted heteroaryl amine derivative and organic electroluminescent device comprising same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102725268A (en) * 2010-01-25 2012-10-10 默克专利有限公司 Compounds for electronic devices
US20150333273A1 (en) * 2014-05-15 2015-11-19 Samsung Electronics Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
CN107663214A (en) * 2016-08-05 2018-02-06 南京高光半导体材料有限公司 A kind of organic high molecular compound and its application
CN108137594A (en) * 2015-07-17 2018-06-08 德山新勒克斯有限公司 Organic electroluminescence device compound, organic electroluminescence device and its electronic device using the compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102725268A (en) * 2010-01-25 2012-10-10 默克专利有限公司 Compounds for electronic devices
US20150333273A1 (en) * 2014-05-15 2015-11-19 Samsung Electronics Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
CN108137594A (en) * 2015-07-17 2018-06-08 德山新勒克斯有限公司 Organic electroluminescence device compound, organic electroluminescence device and its electronic device using the compound
CN107663214A (en) * 2016-08-05 2018-02-06 南京高光半导体材料有限公司 A kind of organic high molecular compound and its application

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110938063A (en) * 2018-09-21 2020-03-31 东进世美肯株式会社 Novel compound for capping layer and organic light emitting device including the same
CN109467556A (en) * 2018-11-16 2019-03-15 烟台九目化学制品有限公司 The preparation and its application on OLED luminescent device of a kind of benzindole diindyl and Acridine derivatives
CN109467556B (en) * 2018-11-16 2021-06-25 烟台九目化学股份有限公司 Preparation of benzandolinoindolacridine derivative and application of benzandolinoindolacridine derivative in OLED (organic light emitting diode) light emitting device
WO2020159099A1 (en) * 2019-02-01 2020-08-06 주식회사 이엘엠 Organic electroluminescent composition and organic electroluminescent element comprising same
WO2020171381A3 (en) * 2019-02-18 2020-10-22 주식회사 이엘엠 Organic electroluminescent composition, and organic electroluminescent element comprising same
WO2021034017A1 (en) * 2019-08-16 2021-02-25 주식회사 엘지화학 Novel compound and organic light emitting device using same
CN113272307A (en) * 2019-08-16 2021-08-17 株式会社Lg化学 Novel compound and organic light emitting device using the same
CN113272307B (en) * 2019-08-16 2023-12-19 株式会社Lg化学 Compound and organic light emitting device using the same
WO2021145429A1 (en) * 2020-01-15 2021-07-22 出光興産株式会社 Compound, material for organic electroluminescent elements, organic electroluminescent element, and electronic device
WO2023022417A1 (en) * 2021-08-20 2023-02-23 주식회사 랩토 Cyano group-substituted heteroaryl amine derivative and organic electroluminescent device comprising same

Similar Documents

Publication Publication Date Title
CN107686484A (en) Organic electroluminescent compounds and the organic electroluminescence device using the compound
CN103254238B (en) New Heteroleptic iridium complex
TWI527875B (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN107663214B (en) A kind of organic compound and its application
EP2521196B1 (en) Organic electroluminescent element
KR100850886B1 (en) Organometalic compounds for electroluminescence and organic electroluminescent device using the same
TWI466980B (en) Organic electroluminescent elements
KR101121677B1 (en) Anthracene derivative and organic electroluminescence device using the same
KR101218029B1 (en) Triphenylene-based compounds that substitute aryl amine compounds and organic electroluminescent device comprising same
JP2013538793A (en) Novel organic electroluminescent compound and organic electroluminescent device containing the same
CN107880056A (en) Organic electroluminescent compounds and the organic electroluminescence device using the compound
TW201105774A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
JP2013526014A (en) Novel organic electroluminescent compound and organic electroluminescent device using the same
TW201329059A (en) Aromatic amine derivative, material for organic electroluminescent element, and organic electroluminescent element
KR20110134581A (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN104471022A (en) Organic light-emitting compound comprising acridine derivatives, and organic light-emitting device comprising same
CN108164511A (en) A kind of organic electroluminescent compounds, organic electroluminescence device and its application
TW201700472A (en) Compound and organic electroluminescence device using the same
KR20140111166A (en) An electroluminescent compound and an electroluminescent device comprising the same
CN108084091A (en) A kind of novel electroluminescent compound and its application and use its organic electroluminescence device
KR101555155B1 (en) Novel spyrobifluorene type organic compounds and an organic electroluminescent device comprising the same
CN108084180A (en) A kind of novel electroluminescent compound and the organic electroluminescence device using the organic electroluminescent compounds
KR20120116884A (en) New compounds and organic light-emitting diode including the same
KR102067415B1 (en) Red Phosphorescent Host Material and Organic Electroluminescent Device Using the Same
CN109535187A (en) Compound and application thereof and organic electroluminescence device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination