CN109309166A - Organic electroluminescence device and contain 2,6,9,10- quaternary anthracene compounds - Google Patents
Organic electroluminescence device and contain 2,6,9,10- quaternary anthracene compounds Download PDFInfo
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Abstract
The present invention relates to the organic electroluminescence device for containing 2,6,9,10- quaternary anthracene compounds, of the invention 2,6,9,10- quaternary anthracene compounds have structure shown in following general formula (1).Since the compound of the present invention has suitable HOMO and a lumo energy, carrier transmission performance more preferably, thus, organic electroluminescence device of the invention has preferably practical performance.Adulterated using the compounds of this invention and LiQ or it is of the invention two kinds it is compound doped as organic electroluminescence device prepared by two-layer electronic transmission layer material can voltage, efficiency and in terms of more preferably property is shown for undoped device.
Description
Technical field
The present invention relates to a kind of organic electroluminescence devices, more particularly to contain 2,6,9,10- quaternary anthracene chemical combination
The organic electroluminescence device of object and 2,6,9,10- quaternary anthracene compounds.
Background technique
Display of organic electroluminescence (hereinafter referred to as OLED) has from main light emission, low-voltage direct-current driving, all solidstate, view
The a series of advantages such as angular width, light-weight, composition and simple process, compared with liquid crystal display, display of organic electroluminescence
Backlight is not needed, visual angle is big, and power is low, and up to 1000 times of liquid crystal display, manufacturing cost is but lower than response speed
The liquid crystal display of same resolution ratio, therefore, organic electroluminescence device has broad application prospects.
As OLED technology is in the continuous propulsion for illuminating and showing two big fields, people are for influencing OLED device performance
The research of efficient organic material focuses more on, an excellent in efficiency service life long organic electroluminescence device be usually device architecture with
The result of the optimization collocation of various organic materials.In the most common OLED device structure, the organic of following type is generally included
Material: hole-injecting material, hole mobile material, electron transport material, and assorted luminescent material (dyestuff or doping visitor
Body material) and corresponding material of main part etc..
Currently, the electron transport material that uses of tradition is Alq3 in electroluminescent device, but the electron mobility ratio of Alq3
It is lower (about 10-6cm2/Vs).In order to improve the electronic transmission performance of electroluminescence device, researcher has done a large amount of exploration
Journal of Sex Research work.LG patent WO03/060956 discloses chemical combination shown in the following formula (a) with benzimidazole ring and anthracene skeleton
Object, there are voltage height, service life insufficient defects for the material.In addition, disclosed in patent KR2015024288A a kind of quinazoline and
The compound of anthracene skeleton, as shown in following formula (b), such material voltage is equally higher, while luminous efficiency is lower.
The leeway however, existing electroluminescent organic material is also improved in terms of luminescent properties, industry need out
The electroluminescent organic material for sending out new and new organic electroluminescence devices
Double-deck or doping type electron transfer layer has had been reported that in the past, compared with conditional electronic transmits layer device,
Device efficiency and in terms of system gone out some advantages, but the improvement in service life is not obvious.Therefore it provides one
The kind organic electroluminescence device that operating voltage is low, luminous efficiency is high is one of target of those skilled in the art.
Summary of the invention
The technical problem to be solved in the present invention is to provide the organic electroluminescences containing 2,6,9,10- quaternary anthracene compounds
Luminescent device, to further increase the luminescent properties of organic electroluminescence device.
Another technical problems to be solved of the invention are to provide the organic electroluminescence that a kind of operating voltage is low, luminous efficiency is high
Luminescent device.
To solve the above problems, present invention research and 2,6,9,10- quaternary anthracene compounds are prepared for, research hair
It is existing, when structure shown in compound has following formula (1), there is suitable HOMO and lumo energy, carrier transmission performance is more
It is good, thus, it applies in OLED device, there is preferably practical performance.It is mixed simultaneously using invention compound with LiQ
Miscellaneous or of the invention two kinds it is compound doped as two-layer electronic transmission layer material in the devices application can voltage,
Efficiency and service life etc. show more preferably property for undoped device.
Organic electroluminescence device generally comprises substrate, and sequentially forms anode layer on the substrate, at least contains
There are the organic function layer and cathode layer of one layer of luminescent layer, the present invention is characterized in that: at least one layer in the organic function layer
Contain the organic electroluminescence device of 2,6,9,10- quaternary anthracene compounds, institute of the present invention individually or as blending constituent
The quaternary anthracene compound in the position 2,6,9,10- stated has structure shown in following general formula (1):
In formula (1), Ar1Selected from substituted or unsubstituted C4~C20Nitrogenous heteroaryl, Ar3Selected from substituted or unsubstituted
Phenyl, naphthalene or xenyl；Ar2Selected from substituted or unsubstituted C6~C12Aryl or fused ring aryl；
Ar1、Ar2Or Ar3It is independent independent selected from C by 0,1 or 21~C4Alkyl, halogen, nitro, cyano, phenyl,
Xenyl, terphenyl, naphthalene, triphenylene, fluorenyl, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, quinolyl, isoquinolin
Base, quinazolyl, quinoxalinyl, cinnoline base, naphthyridines base, triazine radical, pyrido-pyrazine base, furyl, benzofuranyl, hexichol
And furyl, azepine-dibenzofuran group, thienyl, benzothienyl, dibenzothiophene, azepine-dibenzothiophene
Group in group and its composed group replaces；Work as Ar1、Ar2Or Ar3It is described to take when substituent group quantity is 2 or 2 or more
It is same or different for base
Two R1It is independent to be selected from hydrogen, C1~C4Alkyl, halogen, nitro and/or cyano, aryl
Two Ar1It is same or different, as two Ar1When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference；
Two Ar2It is same or different, as two Ar2When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference；
Two Ar3It is same or different, as two Ar3When different, either the type of substituent group either replaces site
It is different to be also possible to substituted structure itself for difference.
In a preferred embodiment of the present invention, the Ar1Selected from following formula group:
Above-mentioned group is independent selected from C by 0,1 or 21~C4Alkyl, halogen, nitro, cyano, phenyl, xenyl, three
Xenyl, naphthalene, triphenylene, fluorenyl, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, quinolyl, isoquinolyl, quinazoline
Base, quinoxalinyl, cinnoline base, naphthyridines base, triazine radical, pyrido-pyrazine base, furyl, benzofuranyl, dibenzofuran group,
Azepine-dibenzofuran group, thienyl, benzothienyl, dibenzothiophene, azepine-dibenzothiophene group and its
Group in composed group replaces, and when substituent group quantity is 2 or 2 or more, the substituent group is same or different.
Ar1Particularly preferably group shown in following formula:
(* indicates link position).
In a preferred embodiment of the present invention, the Ar2Selected from following formula group, phenyl or naphthyl, xenyl；
Optional is independent selected from C by 0,1 or 21~C4Alkyl, halogen, nitro, cyano group replace.
Some specific examples of the compounds of this invention are enumerated below, but these are only example, be not limited effect.
Discovery of the researcher after a large amount of quantum chemical method carries out Structure Selection-experiment-feedback-adjustment structure, anthracene
2,6,9,10 exist simultaneously substituent group, and 2, when 6 connection distinct fragrance substituent groups, can protect the active sites of anthracene nucleus
Point, while capableing of HOMO the and LUMO value of modulating compound, so that the energy level of adjacent layer is preferably matched, in addition, keeping flat altogether
The structure in face is conducive to the film forming of molecule, has both carrier mobility height.Group shown in formula (2)~(16) can induce anthracene bone
The Cloud Distribution of frame moderately expands on substituent group, keeps Cloud Distribution wider, helps to improve carrier mobility, from
And obtain performance more material.
2,6,9,10- quaternary anthracene compound of the present invention may be used as the electron-transport in organic electroluminescence device
Material, it should be noted that when being used as electron transport material, particularly preferably structure shown in A1
Compared with prior art, the compound of the present invention has the advantages that
(1) the compound of the present invention has good electron transport ability, is used as electron transport material, can be preferably
Match with the lumo energy of luminescent layer material of main part, so as to which device operating voltages are effectively reduced and improve the luminous effect of device
Rate extends device lifetime, has very important practical significance in the manufacture of organic electroluminescence device.
(2) this kind of new material in the present invention can be used as electron transport material in efficient OLED device.
(3) preparation is simple for the compounds of this invention, and raw material is easy to get, and is suitable for volume production amplification.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, With reference to embodiment to the present invention make into
One step is described in detail.
Synthetic example:
The compound for the synthetic method that do not mention in the present invention is all the raw produce being obtained through commercial channels.Implement
Various chemicals such as petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, methylene chloride, four chlorinations used in example
Bis- (bromomethyl) benzene of carbon, acetone, 1,2-, CuI, o-phthaloyl chloride, phenylhydrazine hydrochloride, trifluoroacetic acid, acetic acid, trans--diamino
Hexamethylene, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-Fluorenone, sodium tert-butoxide, Loprazolam, 1-
Bromo- 2- methyl naphthalene, o-dibromobenzene, butyl lithium, Bromofume, o-dibromobenzene, benzoyl peroxide, 1- (2- bromophenyl) -2- first
Base naphthalene, N- bromo-succinimide, methoxyl methyl San Jia Ji phosphonium chloride, tris(dibenzylideneacetone) dipalladium, four (triphenylphosphines)
Palladium, 1,3- pairs of 2-phenyl-phosphine oxide nickel chloride, carbazole, 3,6- Dimethylcarbazole, 3- (2- naphthalene) -6- phenyl carbazole, N- phenyl
The basic chemical industries raw materials such as carbazole -3- boric acid, 9- (2- naphthalene) carbazole -3- boric acid chemical products can be commercially available at home.
The synthesis of 1. compound A1 of synthetic example
Nitrogen protection, intermediate M1 (36.5g, 100mmol) and phenyl boric acid (2.30eq), potassium carbonate (5eq), Pd2(dba)3
(2%eq) toluene 1000mL+ ethyl alcohol 500ml+ water 300ml opens stirring, is heated to 100 DEG C of reflux, reacts 12h, reaction solution water
It washes, organic phase is dry, crosses silicagel column, and concentration is boiled with petroleum ether and washed, obtains intermediate M2 (31.2g, yield 85.4%).
Under nitrogen protection, to mechanical stirring is equipped with, 2- (4- bromophenyl) pyridine is added in the 10L there-necked flask of low-reading thermometer
(2.5eq.), tetrahydrofuran 200ml open stirring, and ice ethyl alcohol cryostat, to -90 DEG C to -80 DEG C, 30min is interior to be added dropwise liquid nitrogen cooling
N-BuLi (2.45eq.), -90 DEG C to -80 DEG C of temperature control during dropwise addition are added intermediate M2 (3.62g, 10mmol), finish
Naturally it heats up, removes cryostat, continue stirring 8 hours.Aqueous ammonium chloride solution is added, separates organic phase, dry, toluene is used in concentration
Recrystallization, obtains intermediate M3 (4.8g, 92.3%)
Acetic acid 100ml is added into 250ml reaction flask for nitrogen protection, opens stirring, heating, and reaction solution is warming up to 60 DEG C
Intermediate M3 (5.2g, 10mmol) is added when left and right, KI (5eq.), NaHPO2.H2O (8eq.), flow back (120 DEG C or so) reactions
5 hours.Filtering, with acetic acid, water, ethyl alcohol washes much filtrate.Re crystallization from toluene obtains A1 (4.2g, 87.5%).
The magnetic resonance spectroscopy data of compound A1:
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.56 (s, 1H), 8.35 (s, 1H), 8.28 (s,
2H), 7.98-7.72 (m, 7H), 7.57 (d, J=3.0Hz, 3H), 7.56-7.38 (m, 8H), 7.27 (d, J=12.0Hz, 5H)
The synthesis of 2. compound A2 of synthetic example
Synthesis step is bromo- (2- naphthalene) benzene of the 4-- that 4- bromo biphenyl is replaced with to equivalent with compound A1, difference, instead
After answering, isolated white solid 6.0g, yield 84.5%.
The magnetic resonance spectroscopy data of compound A2:
1H NMR (400MHz, Chloroform) δ 8.97 (s, 3H), 8.45 (d, J=84.0Hz, 5H), 8.35-8.31
(m, 2H), 8.28 (s, 5H), 8.07 (d, J=12.0Hz, 6H), 7.99 (s, 3H), 7.79 (t, J=8.0Hz, 5H), 7.63 (s,
3H), 7.60-7.47 (m, 21H), 7.38 (s, 3H), 7.26 (d, J=12.0Hz, 5H)
The synthesis of 3. compound A-13 of synthetic example
For synthesis step with compound A1, difference is that the 2- bromine that 4- bromo biphenyl is replaced with to equivalent is luxuriant and rich with fragrance, after reaction,
Isolated white solid 6.2g, yield 88.3%.
1H NMR (400MHz, Chloroform) δ 9.11 (s, 1H), 8.97 (s, 1H), 8.70 (s, 1H), 8.56 (s,
1H), 8.43 (s, 1H), 8.35 (s, 1H), 8.28 (s, 2H), 8.15 (s, 1H), 7.91 (d, J=8.0Hz, 2H), 7.84-7.68
(m, 8H), 7.66 (d, J=10.0Hz, 2H), 7.59-7.48 (m, 6H), 7.28 (s, 1H)
The synthesis of 4. compound A4 of synthetic example
With compound A1, difference is to replace with 4- bromo biphenyl into the 2- bromine pyrene of equivalent synthesis step, after reaction,
Isolated white solid 4.6g, yield 75.9%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.46 (d, J=84.0Hz, 2H), 8.34-8.31
(m, 1H), 8.28 (s, 2H), 8.19 (s, 1H), 8.06 (d, J=16.0Hz, 5H), 7.92 (d, J=1.8Hz, 5H), 7.79 (t,
J=8.0Hz, 6H), 7.59-7.47 (m, 6H), 7.28 (s, 1H)
The synthesis of 5. compound A-45 of synthetic example
Synthesis step is with compound A1, and difference is to replace with 4- bromo biphenyl into the bromobenzene of equivalent, by 1- (4- boric acid benzene
Base) -2- phenyl -1H- benzimidazole replaces with 2- (4- phenyl boric acid)-pyrazine of equivalent, after reaction, isolated white
Solid 5.2g, yield 80.0%.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.93–8.86(m,2H),8.86–8.76(m,4H),
8.35 (s, 4H), 7.89 (s, 2H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.41 (s, 2H)
The synthesis of 6. compound A6 of synthetic example
The same compound A-45 of synthesis step, difference are to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole
5- (4- phenyl boric acid)-pyrimidine of equivalent, after reaction, isolated white solid 4.9g, yield 72.4%.
1H NMR(400MHz,Chloroform)δ9.57(s,2H),9.09(s,4H),8.97(s,2H),8.35(s,
2H), 7.65 (s, 4H), 7.54 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H)
The synthesis of 7. compound A7 of synthetic example
With compound A1, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
2- (4- phenyl boric acid) -5- cyanopyrimidine of equivalent, after reaction, isolated white solid 5.2g, yield 78.5%.
1H NMR(400MHz,Chloroform)δ9.29(s,2H),8.97(s,1H),8.35(s,1H),7.96(s,
2H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.41 (s, 2H), 7.25 (s, 2H)
The synthesis of 8. compound A-28 of synthetic example
With compound A7, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
5- (4- phenyl boric acid)-pyrimidine of equivalent, after reaction, isolated white solid 4.9g, yield 72.4%.
1H NMR(400MHz,Chloroform)δ9.57(s,2H),9.09(s,4H),8.97(s,2H),8.35(s,
2H), 7.65 (s, 4H), 7.54 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H)
The synthesis of 9. compound A9 of synthetic example
With compound A1, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
Bis- naphthopyridine of 2- (4- phenyl boric acid) -1,8- of equivalent, after reaction, isolated white solid 4.8g, yield is
75.3%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 2H), 8.69 (d, J=8.0Hz, 4H), 8.37 (d, J=
10.0Hz, 3H), 8.07 (d, J=10.0Hz, 3H), 7.94 (s, 1H), 7.85 (s, 3H), 7.65 (s, 3H), 7.54 (d, J=
12.0Hz,4H),7.41(s,3H).
The synthesis of 10. compound A10 of synthetic example
With compound A1, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
7- (4- phenyl boric acid)-quinoline of equivalent, obtains faint yellow solid 4.7g, yield 73.6%.
1H NMR (400MHz, Chloroform) δ 9.13 (s, 2H), 8.97 (s, 3H), 8.92 (s, 1H), 8.28 (d, J=
10.0Hz, 4H), 8.07 (s, 2H), 7.65 (s, 4H), 7.63-7.44 (m, 9H), 7.40 (d, J=8.0Hz, 3H), 7.25 (s,
8H).
The synthesis of 11. compound A11 of synthetic example
With compound A1, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
2- (4- phenyl boric acid)-quinoline of equivalent, obtains faint yellow solid 5.9g, yield 92.4%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.69 (s, 2H), 8.37 (d, J=16.0Hz, 2H),
8.10 (s, 2H), 8.10 (s, 1H), 8.18-7.79 (m, 4H), 8.18-7.68 (m, 4H), 8.18-7.59 (m, 4H), 8.18-
7.43 (m, 4H), 8.18-7.11 (m, 5H)
The synthesis of 12. compound A12 of synthetic example
With compound A1, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
4, the 6- diphenyl of equivalent--2 boric acid of pyrimidine, obtains faint yellow solid 3.4g, yield 74.5%.
1H NMR (400MHz, Chloroform) δ 8.38 (d, J=12.0Hz, 2H), 8.23 (s, 1H), 7.94 (s, 4H),
7.81(s,1H),7.65(s,2H),7.55(s,6H),7.49(s,2H),7.41(s,2H).
The synthesis of 13. compound A13 of synthetic example
With compound A1, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
3,5- bis- (2- pyridine)-phenyl boric acid of equivalent, obtains faint yellow solid 4.8g, yield 74.5%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.87 (s, 2H), 8.74 (s, 1H), 8.36 (d, J=
8.0Hz, 3H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.39 (d, J=12.0Hz, 3H), 7.14 (s, 2H),
6.90(s,2H).
The synthesis of 14. compound A14 of synthetic example
With compound A1, difference is to replace with 1- (4- boric acid phenyl) -2- phenyl -1H- benzimidazole synthesis step
4- (4- phenyl boric acid)-terpyridyl of equivalent, obtains faint yellow solid 3.2g, yield 75.2%.
1H NMR (400MHz, Chloroform) δ 9.16 (d, J=16.0Hz, 8H), 8.97 (s, 2H), 8.45 (d, J=
80.0Hz, 6H), 7.74 (s, 4H), 7.65 (s, 3H), 7.53 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.24 (d, J=
8.0Hz,12H).
The synthesis of 15. compound A15 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 4, the 6- hexichol of equivalent synthesis step
Base -2- (4- bromophenyl) pyrimidine, after reaction, isolated white solid 6.0g, yield 84.5%.
The magnetic resonance spectroscopy data of compound A2:
1H NMR (400MHz, Chloroform) δ 8.97 (s, 3H), 8.45 (d, J=84.0Hz, 5H), 8.35-8.31
(m, 2H), 8.28 (s, 5H), 8.07 (d, J=12.0Hz, 6H), 7.99 (s, 3H), 7.79 (t, J=8.0Hz, 5H), 7.63 (s,
3H), 7.60-7.47 (m, 21H), 7.38 (s, 3H), 7.26 (d, J=12.0Hz, 5H)
The synthesis of 16. compound 16 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 5- (the 4- bromobenzene of equivalent synthesis step
Base) pyrimidine, after reaction, and isolated white solid 6.2g, yield 88.3%.
1H NMR(400MHz,Chloroform)δ9.11(s,1H),8.97(s,1H),8.70(s,1H),8.56(s,
1H), 8.43 (s, 1H), 8.35 (s, 1H), 8.28 (s, 2H), 8.15 (s, 1H), 7.91 (d, J=8.0Hz, 2H), 7.84-7.68
(m, 8H), 7.66 (d, J=10.0Hz, 2H), 7.59-7.48 (m, 6H), 7.28 (s, 1H)
The synthesis of 17. compound A17 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 2- (the 4- bromobenzene of equivalent synthesis step
Base) -4- phenylquinazoline, after reaction, and isolated white solid 4.6g, yield 75.9%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.46 (d, J=84.0Hz, 2H), 8.34-8.31
(m, 1H), 8.28 (s, 2H), 8.19 (s, 1H), 8.06 (d, J=16.0Hz, 5H), 7.92 (d, J=1.8Hz, 5H), 7.79 (t,
J=8.0Hz, 6H), 7.59-7.47 (m, 6H), 7.28 (s, 1H)
The synthesis of 18. compound A18 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into the 2- phenyl -4- of equivalent synthesis step
(4- bromophenyl) quinazoline, after reaction, isolated white solid 5.2g, yield 80.0%.
1H NMR(400MHz,Chloroform)δ8.97(s,1H),8.93–8.86(m,2H),8.86–8.76(m,4H),
8.35 (s, 4H), 7.89 (s, 2H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.41 (s, 2H)
The synthesis of 19. compound A19 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 2- (the 4- bromobenzene of equivalent synthesis step
Base) -4- (2- pyridyl group) quinazoline, after reaction, and isolated white solid 4.9g, yield 72.4%.
1H NMR(400MHz,Chloroform)δ9.57(s,2H),9.09(s,4H),8.97(s,2H),8.35(s,
2H), 7.65 (s, 4H), 7.54 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H)
The synthesis of 20. compound A20 of synthetic example
Synthesis step is with compound A1, and different to be to replace with phenyl boric acid into the 3- biphenylboronic acid of equivalent, reaction terminates
Afterwards, isolated white solid 5.2g, yield 78.5%.
1H NMR (400MHz, Chloroform) δ 9.29 (s, 2H), 8.97 (s, 1H), 8.35 (s, 1H), 7.96 (s,
2H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.41 (s, 2H), 7.25 (s, 2H)
The synthesis of 21. compound A21 of synthetic example
Synthesis step is with compound A1, and difference is to replace with phenyl boric acid into the 2- biphenylboronic acid of equivalent, by 2- (4- bromine
Phenyl) pyridine replaces with 5- (4- bromophenyl)-pyrimidine of equivalent, after reaction, and isolated white solid 4.9g, yield
It is 72.4%.
1H NMR (400MHz, Chloroform) δ 9.57 (s, 2H), 9.09 (s, 4H), 8.97 (s, 2H), 8.35 (s,
2H), 7.65 (s, 4H), 7.54 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.25 (s, 8H)
The synthesis of 22. compound A22 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 2- (the 4- bromobenzene of equivalent synthesis step
Base) quinoline, phenyl boric acid is replaced with to the 3- fluorobenzoic boric acid of equivalent, after reaction, and isolated white solid 4.8g, yield
It is 75.3%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 2H), 8.69 (d, J=8.0Hz, 4H), 8.37 (d, J=
10.0Hz, 3H), 8.07 (d, J=10.0Hz, 3H), 7.94 (s, 1H), 7.85 (s, 3H), 7.65 (s, 3H), 7.54 (d, J=
12.0Hz,4H),7.41(s,3H).
The synthesis of 23. compound A23 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 2- (the 4- bromobenzene of equivalent synthesis step
Base) quinoline, phenyl boric acid is replaced with to the 4- biphenylboronic acid of equivalent, obtains faint yellow solid 4.7g, yield 73.6%.
1H NMR (400MHz, Chloroform) δ 9.13 (s, 2H), 8.97 (s, 3H), 8.92 (s, 1H), 8.28 (d, J=
10.0Hz, 4H), 8.07 (s, 2H), 7.65 (s, 4H), 7.63-7.44 (m, 9H), 7.40 (d, J=8.0Hz, 3H), 7.25 (s,
8H).
The synthesis of 24. compound A24 of synthetic example
Synthesis step is to replace with phenyl boric acid into the 1- naphthalene boronic acids of equivalent, obtain faint yellow with compound A1, difference
Solid 5.9g, yield 92.4%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.69 (s, 2H), 8.37 (d, J=16.0Hz, 2H),
8.10 (s, 2H), 8.10 (s, 1H), 8.18-7.79 (m, 4H), 8.18-7.68 (m, 4H), 8.18-7.59 (m, 4H), 8.18-
7.43(m,4H),8.18–7.11(m,5H).
The synthesis of 25. compound A25 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into indoles-(the 4- bromine of equivalent synthesis step
Phenyl), phenyl boric acid is replaced with to the 2- naphthalene boronic acids of equivalent, obtains faint yellow solid 3.4g, yield 74.5%.
1H NMR (400MHz, Chloroform) δ 8.38 (d, J=12.0Hz, 2H), 8.23 (s, 1H), 7.94 (s, 4H),
7.81(s,1H),7.65(s,2H),7.55(s,6H),7.49(s,2H),7.41(s,2H).
The synthesis of 26. compound A26 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 2- (the 4- bromobenzene of equivalent synthesis step
Base) quinoline, phenyl boric acid is replaced with to the 2- naphthalene boronic acids of equivalent, obtains faint yellow solid 4.8g, yield 74.5%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.87 (s, 2H), 8.74 (s, 1H), 8.36 (d, J=
8.0Hz, 3H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.39 (d, J=12.0Hz, 3H), 7.14 (s, 2H),
6.90(s,2H).
The synthesis of 27. compound A27 of synthetic example
Synthesis step is with compound A1, and difference is to replace with 2- (4- bromophenyl) pyridine the 2- of equivalent, and (4- is bromo-
2-, 6- difluorophenyl) pyridine, obtain faint yellow solid 3.2g, yield 75.2%.
1H NMR (400MHz, Chloroform) δ 9.16 (d, J=16.0Hz, 8H), 8.97 (s, 2H), 8.45 (d, J=
80.0Hz, 6H), 7.74 (s, 4H), 7.65 (s, 3H), 7.53 (d, J=12.0Hz, 7H), 7.41 (s, 1H), 7.24 (d, J=
8.0Hz,12H).
The synthesis of 28. compound A28 of synthetic example
Synthesis step is with compound A1, and difference is to replace with 2- (4- bromophenyl) pyridine the 2- of equivalent, and (4- is bromo-
2-, 2,5,6- tetrafluoro phenyl) pyridine, obtain faint yellow solid 4.8g, yield 74.5%.
1H NMR (400MHz, Chloroform) δ 8.97 (s, 1H), 8.87 (s, 2H), 8.74 (s, 1H), 8.36 (d, J=
8.0Hz, 3H), 7.65 (s, 2H), 7.54 (d, J=12.0Hz, 4H), 7.39 (d, J=12.0Hz, 3H), 7.14 (s, 2H),
6.90 (s, 2H)
The synthesis of 29. compound A29 of synthetic example
With compound A1, difference is to replace with 2- (4- bromophenyl) pyridine into 2- (the 4- bromo- 2- of equivalent synthesis step
Fluorophenyl) pyridine, obtain faint yellow solid 4.9g, yield 72.1%.
The synthesis of 30. compound A-13 0 of synthetic example
Synthesis step is the same as compound A1, different to be to replace with phenyl into the fluorobenzene of equivalent, 2- (4- bromophenyl) pyrrole
Pyridine replaces with 2- (bromo- -2 phenyl of 2- isopropyl of 4-) pyridine of equivalent, obtains faint yellow solid 5.2g, yield 78.5%.
The synthesis of 31. compound A-13 1 of synthetic example
With compound A1, difference is to replace with phenyl into the ethylphenyl of equivalent synthesis step, obtains pale yellow colored solid
Body 4.5g, yield 74.5%.
The analysis detection of intermediate and compound of the invention uses AB SCIEX mass spectrograph (4000QTRAP) and Brooker
Nuclear Magnetic Resonance (400M).
Table 1: the analysis detecting data of composite structure compound in synthetic example
Structure optimization is carried out to compound using Gauss software, calculation method is that the hydridization of density functional theory (DFT) is general
Letter B3LYP and base group 6-31G (d, p), and the highest for evaluating compound A1, A5, A7, A9, A13 and known compound a, b accounts for
There are molecular orbit (HOMO), lowest unoccupied molecular orbital (LUMO), the results are shown in table 2.
Table 2: the compounds of this invention and documents compound energy level value
It can be seen that the compound in the compounds of this invention and patent KR2015024288A from above-mentioned comparison of computational results
It compares, HOMO and LUMO are deeper, are more advantageous to the effect for playing hole barrier, while can reduce between successive functional layers
Energy system is poor, advantageously reduces the voltage of device；And this patent compound is compared with patent WO03/060956, this patent compound
Active site on parent nucleus is protected, and Thermodynamically stable can improve, and be can be improved the device lifetime of material, is more likely realized
Commercialized purposes, while having the characteristics that HOMO and LUMO are deeper, it can play the role of reducing voltage and hole barrier.
Compared with publication compound, performance has obviously to be improved the compounds of this invention.
Device embodiments:
The structure of organic electroluminescence device of the present invention is preferably as described below the structure of composition:
(1) anode/hole injection layer (HIL)/hole transmission layer (HTL)/luminescent layer (EML)/electron transfer layer (ETL)/
Electron injecting layer (EIL)/cathode；
(2) anode/hole transmission layer (HTL)/luminescent layer (EML)/hole blocking layer (HBL)/electron transfer layer (ETL)/
Electron injecting layer (EIL)/cathode
Above-mentioned "/" indicates to be laminated in order between different function layer.
In the preferred embodiment, organic electroluminescence device has lower operating voltage and higher luminous effect
Rate.
The substrate in conventional organic luminescence organic electroluminescence device can be used in substrate, such as: glass or plastics.Anode
Material can use transparent high conductivity material, such as indium tin oxygen (ITO), indium zinc oxygen (IZO), stannic oxide (SnO2), oxygen
Change zinc (ZnO) etc..Glass substrate is selected in the organic electroluminescence device production of embodiment, ITO makees anode material.
Common hole-injecting material has CuPc, TNATA and PEDT:PSS etc..Organic electroluminescence device of the invention
Hole injection layer uses 2-TNATA.
Hole transmission layer can use N, N '-two (3- tolyl)-N, N '-diphenyl-[1,1- xenyl] -4,4 '-two
Amine (TPD) or N, N '-diphenyl-N, N '-two (1- naphthalene)-(1,1 '-xenyl) -4, the tri-arylamine groups material such as 4 '-diamines (NPB)
Material.Hole mobile material selects NPB in the organic electroluminescence device that the present invention makes.
Organic electroluminescence device structure can be also possible to multi-luminescent layer structure for single-shot photosphere.In the embodiment of the present invention
Using the structure of single-shot photosphere.It include light emitting host material and luminescent dye, wherein luminescent dye and the master that shines in luminescent layer
The mass ratio of body material is controlled by the evaporation rate both regulated and controled in device fabrication process, usually control luminescent dye with
The evaporation rate ratio of light emitting host material is 1% to 8%, preferably 3% to 5%.
Common luminescent dye include metal iridium complex Ir (ppy), FIrpic and pure small organic molecule, rubrene,
DPP, DCJ, DCM etc..
Common light emitting host material includes BAlq, AND, CBP, mCP, TBPe etc..
Common electron transport material has Alq3, Bphen, BCP, PBD etc., and the present invention selects Alq3, formula (a), formula (c) to make
It is compared for electron transport layer materials and the compounds of this invention.
Selected cathode material is LiF/Al in organic electroluminescence device production of the invention.
Different materials specific structure used in the present invention is seen below:
Above-mentioned electroluminescent organic material, those skilled in the art, which are based on known method, can voluntarily prepare or purchase from Chemical market
It buys.
1. the compounds of this invention of device embodiments is used as electron transport material in organic electroluminescence device
The present embodiment prepares 9 organic electroluminescence devices altogether, and structure is, according to " hole injection layer on substrate
(HIL) sequence of/hole transmission layer (HTL)/luminescent layer (EML)/electron transfer layer (ETL)/electron injecting layer (EIL)/cathode "
Stacking, each layer are made of following material:
ITO/2-TNATA (30nm)/NPB (20nm)/CBP:Ir (ppy)3(5%) (20nm)/the compounds of this invention
(50nm)/LiF(1nm)/Al。
When preparing the electron transfer layer of device of the present invention, material selection scheme are as follows: a kind of preferred compounds of the invention or
A kind of preferred compound of the present invention and LiQ are adulterated or two kinds of preferred compounds of the invention adulterate (doping ratio 10:90-
90:10)。
Wherein 4 comparison organic electroluminescence devices, electron transport material select Alq3, formula (a) compound and formula (c) to change
Close object.
Organic electroluminescence device preparation process is as follows in the present embodiment:
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；?
Vacuum evaporation compound N PB on hole injection layer forms the hole transmission layer with a thickness of 20nm, evaporation rate 0.1nm/s；
Luminescent layer of the vacuum evaporation EML as device on hole transmission layer, EML include material of main part and dye materials, using more
The method that source is steamed altogether, adjusting material of main part CBP evaporation rate are 0.1nm/s, and 3 evaporation rate of dye materials Ir (ppy) is according to mixing
Miscellaneous ratio setting, vapor deposition total film thickness are 20nm；
Its evaporation rate is 0.1nm/s to material solution when preparing device electron transfer layer as described above, and total film thickness is deposited
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 3.
Table 3: the driving voltage and current efficiency of organic electroluminescence devices
The device performance of device embodiments 1-1 to 1-15 as disclosed in table 3 and device comparative example 1-1 to 1-5 as it can be seen that
In organic electroluminescence device structure in the identical situation of other materials, carried out using ETL material of the material of the present invention to device
Adjustment, can reduce significantly the operating voltage of device, and increase substantially the luminous efficiency of device.This is with the present invention
Column compound has deeper LUMO value and preferable electron mobility related.In addition, material of the present invention and LiQ doping use
When, under the conditions of different doping ratios, lower device voltage is achieved compared with undoped with embodiment, is able to maintain simultaneously
Under efficiency unanimous circumstances, there is apparent extension in the service life during which；Use is doped using two kinds of compounds of the invention
When, the voltage of device also has apparent reduction compared with undoped with device, and embodiment device also shows the longer service life.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case 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, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (16)
1. a kind of organic electroluminescence device, including substrate, and sequentially forms anode layer on the substrate, at least contains
The organic function layer and cathode layer of one layer of luminescent layer, it is characterised in that: at least one layer in the organic function layer is independent or makees
Contain the compound with structure shown in following logical formula (I) for blending constituent,
In formula (1), Ar1Selected from substituted or unsubstituted C4~C20Nitrogenous heteroaryl, Ar3Selected from substituted or unsubstituted phenyl,
Naphthalene or xenyl；Ar2Selected from substituted or unsubstituted C6~C12Aryl or fused ring aryl；
Ar1、Ar2Or Ar3It is independent independent selected from C by 0,1,2,3,4 or 81~C4Alkyl, halogen, nitro, cyano,
It is phenyl, xenyl, terphenyl, naphthalene, triphenylene, fluorenyl, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, quinolyl, different
Quinolyl, quinazolyl, quinoxalinyl, cinnoline base, naphthyridines base, triazine radical, pyrido-pyrazine base, furyl, benzofuranyl,
Dibenzofuran group, azepine-dibenzofuran group, thienyl, benzothienyl, dibenzothiophene, azepine-dibenzothiophenes
Group in the group of base and its composed group replaces, and works as Ar1、Ar2Or Ar3When substituent group quantity is 2 or 2 or more, institute
It is same or different to state substituent group；
Two R1It is independent to be selected from hydrogen, C1~C4Alkyl, halogen, nitro and/or cyano, aryl；
Two Ar1It is same or different, as two Ar1When different, either the type of substituent group either replaces site not
Together, it is different to be also possible to substituted structure itself；
Two Ar2It is same or different, as two Ar2When different, either the type of substituent group either replaces site not
Together, it is different to be also possible to substituted structure itself；
Two Ar3It is same or different, as two Ar3When different, either the type of substituent group either replaces site not
Together, it is different to be also possible to substituted structure itself.
2. organic electroluminescence device according to claim 1, which is characterized in that Ar1Selected from following formula group:
Above-mentioned group is independent selected from C by 0,1 or 21~C4Alkyl, halogen, nitro, cyano, phenyl, xenyl, terphenyl
Base, naphthalene, triphenylene, fluorenyl, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, quinolyl, isoquinolyl, quinazolyl, quinoline
Quinoline base, cinnoline base, naphthyridines base, triazine radical, pyrido-pyrazine base, furyl, benzofuranyl, dibenzofuran group, azepine-
It dibenzofuran group, thienyl, benzothienyl, dibenzothiophene, azepine-dibenzothiophene group and its is formed
Group in group replace, when substituent group quantity be 2 or 2 or more when, the substituent group is same or different.
3. organic electroluminescence device according to claim 1, which is characterized in that Ar3Selected from phenyl or naphthyl；Preferably,
Work as Ar3When for phenyl, Ar1It is preferably placed at the contraposition of phenyl.
4. organic electroluminescence device according to claim 1, it is characterised in that two Ar1、Ar2And Ar3It is identical.
5. organic electroluminescence device according to claim 1, which is characterized in that the compound is following structural formula A1
One of the compound represented to A16:
It include that hole is infused 6. organic electroluminescence device according to any one of claim 1 to 5, in organic function layer
Enter layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, it is characterised in that: the organic function layer is electronics
Transport layer.
7. organic electroluminescence device according to claim 6, lead to one of compound of structure shown in formula (I) or
Two kinds of combination is separately as one of compound of structure shown in electron transport material use or logical formula (I) or two
The combination of kind and LiQ doping are used as electron transport material.
8. organic electroluminescence device according to claim 7, lead to one of compound of structure shown in formula (I) or
Two kinds of combination and LiQ doping are used as electron transport material, and used doping weight ratio is 90::10-10:90.
9. applying according to claim 8, which is characterized in that electron transport material formed electron transfer layer with a thickness of
10-50nm。
10. one kind contains 2,6,9,10- quaternary anthracene compounds, there is the compound of structure shown in logical formula (I),
In formula (1), Ar1Selected from substituted or unsubstituted C4~C20Nitrogenous heteroaryl, Ar3Selected from substituted or unsubstituted phenyl,
Naphthalene or xenyl；Ar2Selected from substituted or unsubstituted C6~C12Aryl or fused ring aryl；
Ar1、Ar2Or Ar3It is independent independent selected from C by 0,1 or 21~C4Alkyl, halogen, nitro, cyano, phenyl, biphenyl
Base, terphenyl, naphthalene, triphenylene, fluorenyl, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, quinolyl, isoquinolyl, quinoline
Oxazoline base, quinoxalinyl, cinnoline base, naphthyridines base, triazine radical, pyrido-pyrazine base, furyl, benzofuranyl, dibenzo furan
It mutters base, azepine-dibenzofuran group, thienyl, benzothienyl, dibenzothiophene, azepine-dibenzothiophene group
And its group in composed group replaces；, work as Ar1、Ar2Or Ar3When substituent group quantity is 2 or 2 or more, the substitution
Base is same or different
Two R1It is independent to be selected from hydrogen, C1~C4Alkyl, halogen, nitro and/or cyano, aryl；
Two Ar1It is same or different, as two Ar1When different, either the type of substituent group either replaces site not
Together, it is different to be also possible to substituted structure itself；
Two Ar2It is same or different, as two Ar2When different, either the type of substituent group either replaces site not
Together, it is different to be also possible to substituted structure itself；
Two Ar3It is same or different, as two Ar3When different, either the type of substituent group either replaces site not
Together, it is different to be also possible to substituted structure itself.
11. compound according to claim 10, which is characterized in that Ar1Selected from following formula group:
Above-mentioned group is independent selected from C by 0,1 or 21~C4Alkyl, halogen, nitro, cyano, phenyl, xenyl, terphenyl
Base, naphthalene, triphenylene, fluorenyl, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, quinolyl, isoquinolyl, quinazolyl, quinoline
Quinoline base, cinnoline base, naphthyridines base, triazine radical, pyrido-pyrazine base, furyl, benzofuranyl, dibenzofuran group, azepine-
It dibenzofuran group, thienyl, benzothienyl, dibenzothiophene, azepine-dibenzothiophene group and its is formed
Group in group replace, when substituent group quantity be 2 or 2 or more when, the substituent group is same or different.
12. compound according to claim 10, which is characterized in that Ar3Selected from phenyl or naphthyl；Preferably, work as Ar3For
When phenyl, Ar1It is preferably placed at the contraposition of phenyl.
13. compound according to claim 10, it is characterised in that two Ar1、Ar2And Ar3It is identical.
14. compound according to claim 10, which is characterized in that the compound is following structural formula A1 to A16 generation
One of compound of table:
15. compound described in any one of claim 10~14 is as electron transport material in organic electroluminescence device
Application.
16. application according to claim 16, one of compound described in any one of claim 10~14 or
The combination and LiQ doping that two kinds of person are used as electron transport material, and used doping weight ratio is 90::10-10:90.
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| CN111187201A (en) * | 2020-01-22 | 2020-05-22 | 清华大学 | Compound and organic electroluminescent device |
| WO2020215564A1 (en) * | 2019-04-22 | 2020-10-29 | 吉林奥来德光电材料股份有限公司 | Organic light-emitting material and preparation method and application thereof |
| CN113429353A (en) * | 2021-06-25 | 2021-09-24 | 上海钥熠电子科技有限公司 | Naphthyridine derivative-containing compound and application thereof |
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| KR20150024288A (en) * | 2013-08-26 | 2015-03-06 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
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| WO2003060956A2 (en) * | 2002-01-18 | 2003-07-24 | Lg Chem, Ltd. | New material for transporting electrons and organic electroluminescent display using the same |
| KR20150024288A (en) * | 2013-08-26 | 2015-03-06 | 주식회사 엘지화학 | Hetero-cyclic compound and organic light emitting device comprising the same |
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