CN107915732B - Naphthyridines replaces anthracene derivant and organic electroluminescence device - Google Patents
Naphthyridines replaces anthracene derivant and organic electroluminescence device Download PDFInfo
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- CN107915732B CN107915732B CN201711297038.XA CN201711297038A CN107915732B CN 107915732 B CN107915732 B CN 107915732B CN 201711297038 A CN201711297038 A CN 201711297038A CN 107915732 B CN107915732 B CN 107915732B
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- 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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
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- H—ELECTRICITY
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- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H—ELECTRICITY
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- 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
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- 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
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- H—ELECTRICITY
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- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
Abstract
The present invention provides a kind of naphthyridines substitution anthracene derivant, has structure shown in logical formula (I) as follows:, wherein L is selected from chemical bond, substituted or unsubstituted C6~C12Arlydene or sub- condensed-nuclei aromatics group, substituted or unsubstituted C3~C12Inferior heteroaryl or sub- condensed hetero ring aromatic hydrocarbon group；Ar1、Ar2It is respectively and independently selected from substituted or non-substituted C6~C30Aryl or condensed-nuclei aromatics group, substituted or non-substituted C3~C30Heteroaryl or condensed hetero ring aromatic hydrocarbon group；R1、R2、R3、R4It is respectively and independently selected from hydrogen, C1~C10Alkyl, halogen, cyano, nitro, substituted or unsubstituted C6~C30Aryl or condensed-nuclei aromatics group, substituted or unsubstituted C3~C30Heteroaryl or condensed hetero ring aromatic hydrocarbon group.When the naphthyridines replaces anthracene derivant to be used for organic electroluminescent, electron mobility is higher, stability is preferable, while being conducive to evaporation film-forming.
Description
Technical field
The present invention relates to be related to organic field of photovoltaic materials, more particularly to a kind of naphthyridines substitution anthracene derivant and organic electroluminescence
Luminescent device.
Background technique
As OLED technology is in the continuous propulsion for illuminating and showing two big fields, people are for influencing OLED device performance
The research of efficient organic material focus more on.One excellent in efficiency service life OLED device of length is usually that device architecture has with various
The result of the optimization collocation of machine material.In the most common OLED device structure, the organic material of following type is generally included: empty
Hole injection material, hole mobile material, electron transport material, and assorted luminescent material (dyestuff or doping guest materials)
With corresponding material of main part etc..
The electron transport material that tradition uses in electroluminescent device is Alq3(three (8-hydroxyquinoline) aluminium), but Alq3
Electron mobility it is relatively low (about in 10-6cm2/Vs).In order to improve the electronic transmission performance of electroluminescence device, people is studied
Member has done a large amount of pilot study work.But there are still cannot take into account luminous efficiency and OLED device service life at present.
Summary of the invention
The embodiment of the present invention provides that a kind of electron mobility is higher, stability is preferable, while being conducive to the electricity of evaporation film-forming
Sub- transmission material, and the organic electroluminescence device that a kind of operating voltage is low, luminous efficiency is high, the service life is long is provided.
In order to achieve the above object, the invention adopts the following technical scheme.
In a first aspect, the present invention provides a kind of naphthyridines to replace anthracene derivant, there is structure shown in logical formula (I) as follows:
Wherein, L is selected from chemical bond, substituted or unsubstituted C6~C12Arlydene or sub- condensed-nuclei aromatics group, replace or
Unsubstituted C3~C12Inferior heteroaryl or sub- condensed hetero ring aromatic hydrocarbon group；
Ar1、Ar2It is respectively and independently selected from substituted or non-substituted C6~C30Aryl or condensed-nuclei aromatics group, substitution or non-take
The C in generation3~C30Heteroaryl or condensed hetero ring aromatic hydrocarbon group；
R1、R2、R3、R4It is respectively and independently selected from hydrogen, C1~C10Alkyl, halogen, cyano, nitro, substituted or unsubstituted C6
~C30Aryl or condensed-nuclei aromatics group, substituted or unsubstituted C3~C30Heteroaryl or condensed hetero ring aromatic hydrocarbon group.
Second aspect, the embodiment of the present invention provide a kind of organic electroluminescence device, including electron transfer layer, the electronics
It include that at least one naphthyridines provided by the invention replaces anthracene derivant as electron transport material in transport layer.
Naphthyridines provided by the invention replaces anthracene derivant, and precursor structure has good coplanarity, so that the derivative
Carrier transport with higher ensure that luminous efficiency, and be conducive to the film forming of molecule.2 of naphthyridines and anthracene nucleus
It is connected, the active site of parent nucleus can be protected, conducive to the stability for keeping compound.
Replace OLED device of the anthracene derivant as electron transport layer materials using above-mentioned naphthyridines, it is corresponding with higher
Luminous efficiency and longer service life.
Detailed description of the invention
From the detailed description with reference to the accompanying drawing to the embodiment of the present invention, these and/or other aspects of the invention and
Advantage will become clearer and be easier to understand, in which:
Fig. 1 is highest occupied molecular orbital HOMO (the Highest Occupied Molecular of the compounds of this invention A8
Orbital, HOMO highest occupied molecular orbital)；
Fig. 2 is lowest unoccupied molecular orbital LUMO (the Lowest Unoccupied Molecular of the compounds of this invention A8
Orbital, lowest unoccupied molecular orbital)；
Fig. 3 is the highest occupied molecular orbital HOMO of the compounds of this invention A17；
Fig. 4 is the lowest unoccupied molecular orbital LUMO of the compounds of this invention A17.
Specific embodiment
The embodiment of the invention provides a kind of naphthyridines to replace anthracene derivant, the structure with general formula (I):
Wherein:
L is selected from chemical bond, substituted or unsubstituted C6~C12Arlydene or sub- condensed-nuclei aromatics group, substituted or unsubstituted
C3~C12Inferior heteroaryl or sub- condensed hetero ring aromatic hydrocarbon group；
Ar1、Ar2It is respectively and independently selected from substituted or non-substituted C6~C30Aryl or condensed-nuclei aromatics group, substitution or non-take
The C in generation3~C30Heteroaryl or condensed hetero ring aromatic hydrocarbon group；Ar1、Ar2It may be the same or different；
R1、R2、R3、R4It is respectively and independently selected from hydrogen, C1~C10Alkyl, halogen, cyano, nitro, substituted or unsubstituted C6
~C30Aryl or condensed-nuclei aromatics group, substituted or unsubstituted C3~C30Heteroaryl or condensed hetero ring aromatic hydrocarbon group.
Specifically, as the above-mentioned Ar of definition1、Ar2With R3And R4When being respectively and independently selected from aryl, refer to selected from a fixed number
Aromatics ring system of mesh ring skeleton carbon atom, including single ring architecture substituent group such as phenyl etc. also include being covalently attached structure
Aromatic ring substituents group is such as xenyl, terphenyl.
R1、R2、R3And R4Hydrogen, C can be respectively and independently selected from1~C5Alkyl, halogen, cyano, nitro, C6~C15Take
Generation or unsubstituted aryl or condensed-nuclei aromatics group, C3~C15Substituted or unsubstituted heteroaryl or condensed hetero ring aromatic hydrocarbon group.
R1、R2、R3、R4It is being respectively and independently selected from substituted aryl or condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aryl
When group, substituent group thereon can be independently selected from by halogen, cyano, nitro, C1~C10Alkyl or cycloalkyl, C2~C10Alkene
Base, C1~C6Alkoxy or thio alkoxy group, C6~C30Mononuclear aromatics or condensed-nuclei aromatics group, containing selected from N, O,
S, the hetero atom and C of Si6~C30Mononuclear aromatics or condensed-nuclei aromatics group and Si (R5)3The group of composition.Wherein, R5Selected from C1~C6
Alkyl.Further, above-mentioned substituent group can be independently selected from by F, cyano, C1~C5Alkyl or cycloalkyl, Si
(CH3)3, C2~C5Alkenyl, C2~C5Alkoxy or thio alkoxy group.
Work as R1、R2、R3And R4When being respectively and independently selected from substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group, thereon
Hetero atom can be one or more O, S and/or N.
L is selected from the C replaced6~C12Arlydene or sub- condensed-nuclei aromatics group, C3~C12Inferior heteroaryl or sub- thick miscellaneous
When aromatic hydrocarbon group, substituent group thereon can be independently selected from by halogen, cyano, nitro, C1~C10Alkyl or cycloalkanes
Base, C2~C10Alkenyl, C1~C6Alkoxy or thio alkoxy group, C6~C30Mononuclear aromatics or condensed-nuclei aromatics base
The hetero atom and C for being selected from N, O, S, Si are contained in group6~C30Mononuclear aromatics or condensed-nuclei aromatics group and Si (R5)3Composition
Group.Wherein, R5Selected from C1~C6Alkyl.
Ar1、Ar2C can preferably independently be selected from6~C20Substituted or non-substituted aryl or condensed-nuclei aromatics group, C5~
C20Substituted or non-substituted heteroaryl or condensed hetero ring aromatic hydrocarbon group.
Work as Ar1、Ar2It is respectively and independently selected from substituted or non-substituted C3~C30Heteroaryl or condensed hetero ring aromatic hydrocarbon group when,
On hetero atom can be one or more O, S and/or N.
Work as Ar1、Ar2It is respectively and independently selected from substituted aryl or condensed-nuclei aromatics group, heteroaryl or condensed hetero ring aromatic hydrocarbon group
When, substituent group thereon is independently selected from by halogen, cyano, nitro, C1~C10Alkyl or cycloalkyl, C2~C10Alkenyl, C1
~C6Alkoxy or thio alkoxy group, C6~C30Mononuclear aromatics or condensed-nuclei aromatics group, containing be selected from N, O, S, Si
Hetero atom and C6~C30Mononuclear aromatics or condensed-nuclei aromatics group and Si (R5)3The group of composition.Wherein, the R5Selected from C1~C6's
Alkyl.Further, above-mentioned substituent group can be independently selected from by F, cyano, C1~C5Alkyl or cycloalkyl, Si (CH3)3, C2~
C5Alkenyl, C1~C5Alkoxy or thio alkoxy group, C6~C15Mononuclear aromatics or condensed-nuclei aromatics group, containing choosing
From the hetero atom and C of N or O6~C15Mononuclear aromatics or condensed-nuclei aromatics group composition group.
Ar1、Ar2When being respectively and independently selected from substituted or non-substituted aryl or fused ring aryl group, it can be respectively and independently selected from
By phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, indenyl, fluoranthene base, fluorenyl, indeno fluorenyl, triphenylene, pyrene
Base, base,Base, aphthacene base, the phenyl replaced by furyl, thienyl, pyrrole radicals and/or pyridyl group, benzene binaphthyl, 4-
Naphthylphenyl, 6- phenyl napthyl, 7- phenyl phenanthryl.Wherein, above-mentioned xenyl, which can be selected from, 2- xenyl, 3- xenyl, 4-
The group of xenyl composition；Above-mentioned terphenyl can be selected from by p- terphenyl -4- base, p- terphenyl -3- base, p- three
The group of xenyl -2- base, m- terphenyl -4- base, m- terphenyl -3- base and m- terphenyl -2- base composition；It is above-mentioned
Naphthalene can be selected from the group as composed by 1- naphthalene and 2- naphthalene；Above-mentioned anthryl can be selected from by 1- anthryl, 2- anthryl and 9- anthracene
Group composed by base；Above-mentioned fluorenyl is selected from the group as composed by 1- fluorenyl, 2- fluorenyl, 3- fluorenyl, 4- fluorenyl and 9- fluorenyl；It is above-mentioned
Fluorenyl derivative is selected from by 9,9 '-dimethyl fluorenes, group composed by 9,9 '-spiral shell, two fluorenes and benzfluorene；Above-mentioned pyrenyl is selected from by 1-
Group composed by pyrenyl, 2- pyrenyl and 4- pyrenyl；Above-mentioned aphthacene base is selected from by 1- aphthacene base, 2- aphthacene base and 9- and four
Group composed by phenyl.
Ar1、Ar2In the heteroaryl groups or condensed hetero ring aromatic hydrocarbon group being respectively and independently selected from, can be independently selected from by furans
Base, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, naphthyridines base, quinoline
Quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzo naphthyridines, isobenzofuran-base, indyl, benzo quinoline
Diazole, the coffee that quinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, phenyl replace
The group of quinoline base, coffee quinoline benzothiazolyl and benzodioxole group composition.Wherein, above-mentioned carbazole radical derivative can be selected from
The group being made of 9- phenyl carbazole, 9- naphthyl carbazole benzo carbazole, dibenzo-carbazole and indolocarbazole.
Further, Ar1、Ar2Phenyl, phenyl that phenyl, xenyl, naphthalene, pyridyl group replace can be respectively and independently selected from
Pyridyl group, anthryl, phenanthryl, furyl, benzofurane base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base or pyridine
Base.
R1、R2、R3And R4Following radicals can be respectively and independently selected from: methyl, ethyl, propyl, isopropyl, tert-butyl, ring penta
Base, cyclohexyl, cyano, nitro, phenyl, naphthalene, triphenylene, 9,9 dimethyl fluorenes, two fluorenyl of spiral shell, furyl, benzofurane
Base, thienyl, tolylthiophene base, pyrrole radicals, phenylpyrrole base, pyridyl group, phenylpyridyl, naphthyridines base, fluorenyl, indenofluorene
Base, quinoline, triazine radical, benzofuranyl, benzothienyl, phentriazine, benzo naphthyridines, isobenzofuran-base, indyl, benzene
And quinoline, dibenzofuran group, dibenzothiophene, dibenzopyrrole base, carbazyl and its derivative, phenyl replace two
Azoles, coffee quinoline base, coffee quinoline benzothiazolyl or benzodioxole group.Wherein, above-mentioned carbazole radical derivative can selected from by
9- phenyl carbazole, 9- naphthyl carbazole benzo carbazole, the group of dibenzo-carbazole and indolocarbazole composition.
Further, R1、R2、R3And R4Methyl, ethyl, propyl, isopropyl, tert-butyl, benzene can be respectively and independently selected from
Base, naphthalene, pyridyl group, phenylpyridyl, dibenzofuran group or xenyl.
Compared with prior art, the naphthyridines of general formula (I) of the present invention replaces the advantages of anthracene derivant to embody in the following areas:
Body structure has good coplanarity, so that derivative carrier transport with higher, so as to
Significantly reduce the operating voltage of the device using such material.2 of naphthyridines and anthracene nucleus are connected, and design in this way can protect mother
The active site of core, conducive to the stability of compound is kept, while may insure Cloud Distribution on parent nucleus, LUMO distribution with
Cloud Distribution is consistent.
Precursor structure has deeper LUMO, realizes the performance of good transmission electronics, while keeping coplanar knot
Structure is conducive to the film forming of molecule；The change for replacing ground level and electronic property, can finely tune the energy of final goal compound
Grade and transmission performance, such compound are used as electron transport layer materials, can improve the luminous efficiency of device significantly.
In an embodiment of the present invention, general formula (I) naphthyridines replace anthracene derivant, molecular weight be 1000 or less.It is excellent
It is selected as 450~900.Further preferably 600~800.The substituent group that can be suitable for based on the setting selection of molecular weight.
The naphthyridines of the general formula (I) of molecular weight control in the above range replaces anthracene derivant, and molecular weight is sufficiently large, guarantees
Tg (glass transition temperature) with higher, to have good thermal stability；Meanwhile molecular weight is again no excessive, can be conducive to
Vacuum evaporation film forming.
Specifically, the naphthyridines of general formula (I) replaces the compound group that anthracene derivant can be A1-A21 selected from following structural formula
At group:
Replace anthracene derivant corresponding with above-mentioned naphthyridines provided by the invention, the embodiment of the invention also provides one kind to have
Organic electroluminescence devices include that above-mentioned naphthyridines replaces anthracene derivant in the electron transfer layer of the organic electroluminescence device.
In addition, the device may also include first electrode, second electrode and between the first electrode and second electrode
One or more layers organic layer.Include electron transfer layer in the organic layer, includes provided by the invention above-mentioned in electron transfer layer
The above-mentioned logical formula (I) compound represented of at least one.
Organic electroluminescence device provided by the invention, electron transport layer materials select the naphthyridines of above-mentioned logical formula (I)
Replace anthracene derivant, can be effectively reduced device operating voltages and improve device light emitting efficiency, extends device lifetime.
Further, OLED device provided in an embodiment of the present invention can have the following structure on substrate:
(1) anode/hole injection layer (HIL)/hole transmission layer (HTL)/luminescent layer (EML)/electron transfer layer (ETL)/
Electron injecting layer (EIL)/cathode；
(2) anode/hole transmission layer (HTL)/luminescent layer (EML)/hole blocking layer (HBL)/electron transfer layer (ETL)/
Electron injecting layer (EIL)/cathode.
Above-mentioned "/" indicates to be laminated in order between different function layer.
Traditional substrate having in OLED device can be used in substrate, such as: glass or plastics.Anode material can be using saturating
Bright high conductivity material, such as indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), zinc oxide (ZnO) etc..?
Glass substrate is selected in the OLED device production of one embodiment of the invention, and ITO is selected to make anode material.
Hole-injecting material has CuPc, TNATA and PEDT:PSS etc..Of the invention has in an embodiment, hole injection layer
Using 2-TNATA.
Hole transmission layer can use N, N '-two (3- tolyl)-N, N '-diphenyl-[1,1- xenyl] -4,4 '-two
The tri-arylamine groups material such as amine (TPD) or N, N '-diphenyl-N, N '-two (1- naphthalene)-(1,1 '-xenyl) -4,4 '-diamines (NPB)
Material.Of the invention has in an embodiment, and hole mobile material selects NPB.
OLED device structure can be also possible to multi-luminescent layer structure for single-shot photosphere.It is used in one embodiment of the invention
The structure of single-shot photosphere.It include light emitting host material and luminescent dye, wherein luminescent dye and light emitting host material in luminescent layer
Mass ratio controlled by the evaporation rate both regulated and controled in device fabrication process, usually control luminescent dye and the master that shines
The evaporation rate ratio of body material is 1% to 8%, such as 1%, 2%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%
Deng preferably 3% to 5%.
Wherein, luminescent dye may include metal iridium complex Ir (ppy), FIrpic and pure small organic molecule, it is red glimmering
Alkene, DPP, DCJ, DCM etc..Light emitting host material may include BAlq, AND, CBP, mCP, TBPe etc..
In the OLED device of the embodiment of the present invention, luminescent layer with a thickness of 5nm-50nm, such as 5nm, 6nm, 8nm,
10nm, 12nm, 15nm, 20nm, 25nm, 28nm, 30nm, 35nm, 38nm, 40nm, 45nm, 50nm etc..Preferably 10nm-
30nm.Electron transfer layer of the invention can be used alone a kind of electron transport material provided by the invention, can also cooperate this
The other kinds of electron transport material provided is provided or other conventional electron transport materials of this field are adulterated and used.It is common
Electron transport material have Alq3, code name is material of CA, CC-1 etc. in Bphen, BCP, PBD and the following figure.Have at one
In body embodiment, use can be doped using electron transport material and 8-hydroxyquinoline lithium of the invention.
When a kind of electron transport material of the invention cooperates another electron transport material of the invention or cooperates other
Conventional electron transport material doping in use, the weight ratio of the two can be 90:10-10:90, such as 10:90,20:80,
30:70、40:60、50:50、60:40、70:30、80:20、90:10。
The thickness of electron transfer layer can be 5-100nm, such as 5nm, 6nm, 8nm, 10nm, 12nm, 15nm, 20nm,
30nm, 35nm, 38nm, 40nm, 50nm, 60nm, 80nm, 90nm, 95nm, 100nm etc..Preferably 10-40nm.
The electron injecting layer of OLED device/cathode material selects LiF/Al.
The specific structure of different materials in materials set forth above is seen below:
Organic electroluminescence device of the invention has excellent photoelectricity performance, have relatively low device rise it is bright and
Operating voltage, while there is relatively high luminous efficiency, and device lasts a long time.
The naphthyridines provided in order to better illustrate the present invention replaces anthracene derivant and OLED device, and specific implementation is set forth below
Example is explained.
Illustrate: various chemicals used in synthetic example chemical products can be commercially available at home；The present invention
In the compound of synthetic method do not mentioned be all the raw produce being obtained through commercial channels；Intermediate in the present invention and
The analysis detection of compound uses AB SCIEX mass spectrograph (4000QTRAP) and Brooker Nuclear Magnetic Resonance (400M).
The synthesis of 1 compound A1 of synthetic example
Raw material N1 (13.5g, 0.01mol) and N2 (19.9g, 0.01mol) are placed in toluene, are added catalytic amount (3%eq)
P-methyl benzenesulfonic acid is heated to reflux a point water, reacts about 12h, and reaction solution concentration is added ethyl alcohol, there is yellow powder precipitation, filters, obtain
To intermediate N3.
Intermediate N3 (22.1g, 0.01mol) is placed in dilute hydrochloric acid, is added hydrogen bromide (30g, 0.012mol), room temperature stirs
It mixes, reacts 12h, reaction solution is added to the water, ethyl acetate extraction, and organic phase concentration by column chromatography for separation, obtains intermediate
N4。
Under nitrogen protection, 2- bromo anthraquinone M1 (26.5g, 0.01mol), pinacol borate (0.015mol), Pd (dppf)
Cl2(1%), potassium carbonate mixing is dissolved in 500ml toluene, is heated to flowing back, and overnight, reaction fluid column chromatographs, concentration, petroleum ether for reaction
It boils and washes, obtain intermediate M2 (20.1g, yield 89.6%).
Under nitrogen protection, to equipped with mechanical stirring device there-necked flask in be added intermediate M2 (6.7g, 22mmol,
1.1eq), intermediate N4 (1eq), potassium carbonate (5eq), Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+300ml water,
Stirring is opened, is heated to flowing back, reacts 8h.Organic phase silica gel column chromatography, concentration, obtains yellow powder M3 with re crystallization from toluene
(9.0g, 93.7%).
Under nitrogen protection, (25mmol) 2- bromonaphthalene is dissolved in tetrahydrofuran, and ice ethanol bath is down to -78 DEG C, and n-BuLi is added dropwise
Solution keeps cryogenic conditions, is added dropwise, temperature control 30min, intermediate M3 (4.8g, 10mmol) is dissolved in tetrahydrofuran, drips
It is added in reaction flask, is added dropwise, heat up naturally, react 8h.Dilute hydrochloric acid is added in reaction solution, is extracted with ethyl acetate, it is organic
It is mutually concentrated, solid is precipitated, and intermediate M4 (4.8g, 93.1%) is obtained by filtration.
Intermediate M4 (5.1g, 10mmol) is added in reaction flask, and 100ml glacial acetic acid is added, and potassium iodide is added
(20mmol) is added hypophosphorous acid hydrogen sodium (20mmol), is heated to flowing back, react 5h.Filtering, with water, ethanol rinse, collection is obtained
Yellow powder A1 (5.3g, 79.1%).
The magnetic resonance spectroscopy data of compound A1:
1H NMR(400MHz,CDCl3) δ 8.79 (d, J=12.0Hz, 2H), 8.39 (d, J=2.6Hz, 2H), 8.31
(s,1H),8.20(s,2H),8.16–8.04(m,5H),7.99(s,2H),7.63(s,2H),7.60– 7.51(m,6H),7.39
(d, J=12.0Hz, 4H), 7.19 (s, 4H)
The synthesis of 2. compound A4 of synthetic example
Under nitrogen protection, to equipped with mechanical stirring device there-necked flask in be added intermediate M (9.4g, 22mmol,
1.1eq), intermediate N4 (1eq), potassium carbonate (5eq), Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+300ml water,
Stirring is opened, is heated to flowing back, reacts 8h.Organic phase silica gel column chromatography, concentration, obtains yellow powder M1 with re crystallization from toluene
(9.0g, 93.7%).
Under nitrogen protection, intermediate M1 (4.6g, 10mmol, 1eq) is dissolved in 100ml chloroform, and 1.1eqNBS (N- bromine is added
For succinimide), stirring at normal temperature reacts about 30min, and water is added in reaction solution, stir, liquid separation, organic phase concentration, obtains
Mesosome M2.
Under nitrogen protection, intermediate M2 (10mmol, 1eq), 1- naphthalene are added into the there-necked flask equipped with mechanical stirring device
Boric acid (1eq), potassium carbonate (5eq), Pd (Pph3) 4 (2%), toluene 1000ml+ ethyl alcohol 500ml+300ml water open stirring,
It is heated to flowing back, reacts 8h.Organic phase silica gel column chromatography, concentration, obtains yellow powder A4 with re crystallization from toluene
The magnetic resonance spectroscopy data of compound A4:
1H NMR(400MHz,CDCl3) δ 8.91 (d, J=8.0Hz, 2H), 8.50 (s, 1H), 8.32 (d, J=8.0Hz,
3H), 8.20 (s, 2H), 8.15-8.02 (m, 4H), 8.00 (s, 2H), 7.92 (dd, J=12.4,6.8 Hz, 4H), 7.78 (d, J
=4.0Hz, 2H), 7.63 (s, 1H), 7.60-7.46 (m, 6H), 7.43-7.31 (m, 3H)
The synthesis of 3 compound A11 of synthetic example
Under nitrogen protection, intermediate N1 (28.7g, 0.1mol, 1eq), intermediate ethyl-boron dihydroxide are added in there-necked flask
(1eq), potassium carbonate (5eq), Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+300ml water is opened stirring, is heated to
8h is reacted in reflux.Organic phase silica gel column chromatography, concentration, obtains yellow powder N2 (25.8g, 92.6%) with re crystallization from toluene.
Under nitrogen protection, in there-necked flask be added intermediate N2 (0.1mol, 1eq), 2- phenyl -4- bromobenzeneboronic acid (1eq),
Potassium carbonate (5eq), Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+300ml water opens stirring, is heated to flowing back, instead
Answer 8h.Organic phase silica gel column chromatography, concentration, obtains yellow powder N3 (15.3g, 75.1%) with re crystallization from toluene.
Under nitrogen protection, 2- bromo anthraquinone M1 (26.5g, 0.01mol), pinacol borate (0.015mol), Pd (dppf)
Cl2(1%), potassium carbonate mixing is dissolved in 500ml toluene, is heated to flowing back, and overnight, reaction fluid column chromatographs, concentration, petroleum ether for reaction
It boils and washes, obtain intermediate M2 (20.1g, yield 89.6%).
Under nitrogen protection, to equipped with mechanical stirring device there-necked flask in be added intermediate M2 (6.7g, 22mmol,
1.1eq), intermediate N3 (1eq), potassium carbonate (5eq), Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+300ml water,
Stirring is opened, is heated to flowing back, reacts 8h.Organic phase silica gel column chromatography, concentration, obtains yellow powder M3 with re crystallization from toluene
(9.0g, 93.7%).
Under nitrogen protection, bromobenzene (25mmol) is dissolved in tetrahydrofuran, ice ethanol bath is down to -78 DEG C, and n-BuLi is added dropwise
Solution keeps cryogenic conditions, is added dropwise, temperature control 30min, intermediate M3 (4.8g, 10mmol) is dissolved in tetrahydrofuran, drips
It is added in reaction flask, is added dropwise, heat up naturally, react 8h.Dilute hydrochloric acid is added in reaction solution, is extracted with ethyl acetate, it is organic
It is mutually concentrated, solid is precipitated, and intermediate M4 (4.8g, 93.1%) is obtained by filtration.
Intermediate M4 (5.1g, 10mmol) is added in reaction flask, and 100ml glacial acetic acid is added, and potassium iodide is added
(20mmol) is added hypophosphorous acid hydrogen sodium (20mmol), is heated to flowing back, react 5h.Filtering, with water, ethanol rinse, collection is obtained
Yellow powder A11 (5.3g, 79.1%).
The magnetic resonance spectroscopy data of compound A11:
1H NMR(400MHz,CDCl3) δ 8.99 (s, 2H), 8.54 (s, 2H), 8.37 (s, 2H), 8.24 (t, J=
22.0Hz, 7H), 8.18 (d, J=4.1Hz, 1H), 8.11 (s, 2H), 7.79 (s, 4H), 7.63 (d, J=14.4 Hz, 10H),
7.59–7.37(m,26H),7.35(s,2H),3.40(t,4H),1.30(t,6H).
The synthesis of 4 compound A17 of synthetic example
Under nitrogen protection, intermediate N1 (1eq), 2- pyridine boronic acid are added into the there-necked flask equipped with mechanical stirring device
(1eq), potassium carbonate (5eq), Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+ water 300ml opens stirring, is heated to
8h is reacted in reflux.Organic phase silica gel column chromatography, concentration, obtains yellow powder N2 (9.0g, 93.7%) with re crystallization from toluene.
Under nitrogen protection, by N2 (26.5g, 0.01mol), pinacol borate (0.015mol), Pd (dppf) Cl2
(1%), potassium carbonate mixing is dissolved in 500ml toluene, is heated to flowing back, and reaction is overnight.Fluid column chromatography, concentration are reacted, petroleum ether boils
It washes, obtains intermediate N3 (20.1g, yield 89.6%).
Under nitrogen protection, intermediate 2- bromo anthraquinone (1eq), phenyl boric acid are added into the there-necked flask equipped with mechanical stirring device
(1eq), potassium carbonate 5eq, Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+ water 300ml opens stirring, is heated to back
Stream reacts 8h.Organic phase silica gel column chromatography, concentration, obtains yellow powder M1 (9.0g, 93.7%) with re crystallization from toluene.
Under nitrogen protection, intermediate M1 (4.6g, 10mmol, 1eq) is dissolved in 100ml chloroform, and 1.1eqNBS is added, and room temperature stirs
It mixes, reacts about 30min, water is added in reaction solution, stir, liquid separation, organic phase concentration obtains intermediate M2.
Under nitrogen protection, intermediate M2 (1eq), intermediate N3 are added into the there-necked flask equipped with mechanical stirring device
(1eq), potassium carbonate (5eq), Pd (Pph3)4(2%), toluene 1000ml+ ethyl alcohol 500ml+ water 300ml opens stirring, is heated to
8h is reacted in reflux.Organic phase silica gel column chromatography, concentration, obtains yellow powder M3 (9.0g, 93.7%) with re crystallization from toluene.
Under nitrogen protection, 2- bromonaphthalene (25mmol) is dissolved in tetrahydrofuran, ice ethanol bath is down to -78 DEG C, and normal-butyl is added dropwise
Lithium solution keeps cryogenic conditions, is added dropwise, temperature control 30min, intermediate M3 (4.8g, 10 mmol) is dissolved in tetrahydrofuran,
It is added dropwise in reaction flask, is added dropwise, heat up naturally, react 8h.Dilute hydrochloric acid is added in reaction solution, is extracted with ethyl acetate, has
Machine is mutually concentrated, and solid is precipitated, and intermediate M4 (4.8g, 93.1%) is obtained by filtration.
Intermediate M4 (5.1g, 10mmol) is added in reaction flask, 100ml glacial acetic acid is added, potassium iodide is added
(20mmol) is added hypophosphorous acid hydrogen sodium (20mmol), is heated to flowing back, react 5h.Filtering, with water, ethanol rinse, collection is obtained
Yellow powder A17 (5.3g, 79.1%).
The magnetic resonance spectroscopy data of compound A17:
1H NMR(400MHz,CDCl3) δ 9.15 (dd, J=12.4,8.0Hz, 4H), 8.96 (s, 1H), 8.96 (s,
1H), 8.58-8.52 (m, 2H), 8.39-8.20 (m, 4H), 8.08 (d, J=12.0Hz, 4H), 7.99 (s, 3H), 7.77-
7.69 (m, 3H), 7.67-7.57 (m, 5H), 7.52 (d, J=24.0Hz, 4H), 7.39 (d, J=12.0Hz, 3H), 7.23 (s,
1H).
The Elemental analysis data of compound A1-A21
Using above-mentioned synthetic method and similar synthetic method, the compound of above-mentioned A1-A21 is synthesized, their element
Analysis detecting data arranges in table 1 below:
The elemental analysis result of 1 compound A1-A21 of table
The device embodiments 1-9 of OLED
The structure of this OLED device embodiment 1-9 is, according to " hole injection layer (HIL)/hole transmission layer on substrate
(HTL) sequence of/luminescent layer (EML)/electron transfer layer (ETL)/electron injecting layer (EIL)/cathode " is laminated, each layer it is specific
Material are as follows:
ITO/2-TNATA (30nm)/NPB (20nm)/CBP:Ir (ppy)3(5%) (20nm)/electron transport material
(50nm)/LiF(1nm)/Al。
Wherein, as shown in table 2, electron transport material can only select one or more electron-transport materials provided by the invention
Material can also use electron transport material and other kinds of electron transport material doping of the invention.
Device comparative example 1-4
If table 2 with above-mentioned device embodiments 1-9 in order to compare, the present invention also provides device comparative example 1-4.Device
The structure of part comparative example 1-4 is identical as device embodiments 1-9, and difference is only being selected in the prior art with electron transport material
Common electron transport material.
OLED device embodiment 1-9 and the preparation process of device comparative example 1-4 are as follows:
The glass substrate that surface is coated with transparent conductive film is cleaned by ultrasonic in cleaning solution, in deionized water
Ultrasonic treatment, in ethyl alcohol: ultrasonic oil removing in acetone mixed solution is baked under clean environment and completely removes moisture, use is ultraviolet
Lamp performs etching and ozone treatment, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5~9 × 10-3Pa, above-mentioned
Vacuum evaporation 2-TNATA on anode tunic, adjusting evaporation rate are 0.1nm/s, form the hole injection layer with a thickness of 30nm.
The vacuum evaporation compound N PB on hole injection layer, forms the hole transmission layer with a thickness of 20nm, and evaporation rate is
0.1nm/s.Luminescent layer of the vacuum evaporation EML as device on hole transmission layer, EML include material of main part and dyestuff material
Material, the method steamed altogether using multi-source, adjusting material of main part CBP evaporation rate are 0.1nm/s, dye materials Ir (ppy)3Vapor deposition speed
Rate is set according to doping ratio, and vapor deposition total film thickness is 20nm.
Material solution when preparing device electron transfer layer is as described above, its evaporation rate is 0.1nm/s, vapor deposition total film thickness
For 50nm.
On electron transfer layer (ETL) vacuum evaporation with a thickness of the LiF of 1nm as electron injecting layer, with a thickness of 150nm's
The Al layers of cathode as device.
To gained organic electroluminescence device in same brightness (10000cd/m2) under measure driving voltage and current efficiency,
Performance is shown in Table 2.
Driving voltage, current efficiency and LT90 of the ETL of each OLED device of table 2 under same brightness
As can be seen from Table 2, the ETL material in device is not using in OLED device structure in the identical situation of other materials
Same compound, compared with device comparative example 1-4, device embodiments 1-9 of the invention reduces the operating voltage of device significantly,
And device current efficiency is increased substantially, to improve the luminous efficiency of device；The brightness of OLED decays to 90% from 100%
The time LT90 of Shi Suoyong is significantly improved, that is, extends the service life of OLED device layer.
Above-mentioned significantly higher performance possessed by device embodiments of the invention is originated from its electron transfer layer material used
The characteristic of material.Ideal electron transport material, it should the characteristic with following several respects: first, HOMO and lumo energy close
Suitable, electron mobility is high；The second, thermal stability is high, needs molecular weight sufficiently large, guarantees Tg with higher；Third, film forming
It is good, it forms a film in order to be conducive to vacuum evaporation, molecular weight cannot be too big.Firstly, relative to Alq3And CA, electronics provided by the invention
Layer material is transmitted, coplanarity is good, so that electron-transport rate is high.Secondly, 2 and 6, the active site of anthracene nucleus does not have in CC-1
Substituted base protection, so that the material is perishable under the high temperature conditions, to influence luminous efficiency and service life；And it is of the invention
The electron transport material of offer protects active site in 2 or 2 and 6 substds, thermal stability is improved, to send out
Light efficiency is higher, lasts a long time.
In addition, material of the present invention is adulterated mutually or adulterated from LiQ in use, under the conditions of different doping ratios, and not
Doping embodiment, which is compared, achieves lower device voltage, while being able to maintain under efficiency unanimous circumstances, the service life during which
There is apparent extension.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by those familiar with the art, all answers
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be subject to the protection scope in claims.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.In addition, any group can also be carried out between a variety of different embodiments of the invention
It closes, as long as it does not violate the idea of the present invention, it should also be regarded as the disclosure of the present invention.
Claims (8)
1. a kind of organic electroluminescence device, including electron transfer layer, which is characterized in that include at least in the electron transfer layer
A kind of naphthyridines replaces anthracene derivant as electron transport material；
The naphthyridines replaces anthracene derivant to be selected from the group being made of the compound that following structural formula is A1-A21:
2. organic electroluminescence device according to claim 1, which is characterized in that the naphthyridines replaces anthracene derivant to be selected from
The group formed by having the following structural formula compound:
3. organic electroluminescence device according to claim 1, which is characterized in that the naphthyridines replaces anthracene derivant to be selected from
The group formed by having the following structural formula compound:
4. organic electroluminescence device according to claim 1, which is characterized in that the naphthyridines replaces anthracene derivant to be selected from
The group formed by having the following structural formula compound:
5. organic electroluminescence device described in any one of -4 according to claim 1, which is characterized in that the electron transfer layer
It further include 8-hydroxyquinoline lithium.
6. organic electroluminescence device according to claim 5, which is characterized in that the naphthyridines in the electron transfer layer takes
It is 90:10-10:90 for the doping weight ratio of anthracene derivant and 8-hydroxyquinoline lithium.
7. organic electroluminescence device described in any one of -4 according to claim 1, which is characterized in that the electron transfer layer
It is middle to replace one of anthracene derivant compound to replace other compounds in anthracene derivant to mix with the naphthyridines naphthyridines
Miscellaneous use.
8. organic electroluminescence device described in any one of -4 according to claim 1, which is characterized in that the electron transfer layer
It is middle to replace anthracene derivant and another naphthyridines that anthracene derivant doping is replaced to use a kind of naphthyridines, the weight ratio of the two
Example is 90:10-10:90.
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| PCT/CN2018/095228 WO2019011261A1 (en) | 2017-07-12 | 2018-07-11 | Naphthyridine substituted anthracene derivative and organic electroluminescent device |
| KR1020207002207A KR102391160B1 (en) | 2017-07-12 | 2018-07-11 | Naphthyridine-substituted anthracene derivative and organic electroluminescent device |
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| KR20140082437A (en) * | 2012-12-24 | 2014-07-02 | 에스에프씨 주식회사 | Antracene derivatives having heteroaryl substituted phenyl group and organic light-emitting diode including the same |
| CN105143186A (en) * | 2013-02-22 | 2015-12-09 | 出光兴产株式会社 | Anthracene derivative, material for organic electroluminescent element, and electronic device |
| CN105321984A (en) * | 2014-08-01 | 2016-02-10 | 乐金显示有限公司 | Organic light emitting display device |
| CN106279148A (en) * | 2015-05-22 | 2017-01-04 | 上海和辉光电有限公司 | Promote OLED high temperature, the material of high current density performance and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20140082437A (en) * | 2012-12-24 | 2014-07-02 | 에스에프씨 주식회사 | Antracene derivatives having heteroaryl substituted phenyl group and organic light-emitting diode including the same |
| CN105143186A (en) * | 2013-02-22 | 2015-12-09 | 出光兴产株式会社 | Anthracene derivative, material for organic electroluminescent element, and electronic device |
| CN105321984A (en) * | 2014-08-01 | 2016-02-10 | 乐金显示有限公司 | Organic light emitting display device |
| CN106279148A (en) * | 2015-05-22 | 2017-01-04 | 上海和辉光电有限公司 | Promote OLED high temperature, the material of high current density performance and application thereof |
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