CN115332456A - Organic electroluminescent material composition and application thereof - Google Patents
Organic electroluminescent material composition and application thereof Download PDFInfo
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- CN115332456A CN115332456A CN202110506135.5A CN202110506135A CN115332456A CN 115332456 A CN115332456 A CN 115332456A CN 202110506135 A CN202110506135 A CN 202110506135A CN 115332456 A CN115332456 A CN 115332456A
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims description 57
- 150000001875 compounds Chemical class 0.000 claims abstract description 89
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 96
- -1 nitro, hydroxyl Chemical group 0.000 claims description 37
- 125000001072 heteroaryl group Chemical group 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000001769 aryl amino group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002346 layers by function Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 5
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- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 3
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- 125000005580 triphenylene group Chemical group 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
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- 238000002347 injection Methods 0.000 abstract description 19
- 239000007924 injection Substances 0.000 abstract description 19
- 230000005540 biological transmission Effects 0.000 abstract description 6
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical group C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 abstract description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 20
- 229910000027 potassium carbonate Inorganic materials 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
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- NSGDYZCDUPSTQT-UHFFFAOYSA-N N-[5-bromo-1-[(4-fluorophenyl)methyl]-4-methyl-2-oxopyridin-3-yl]cycloheptanecarboxamide Chemical compound Cc1c(Br)cn(Cc2ccc(F)cc2)c(=O)c1NC(=O)C1CCCCCC1 NSGDYZCDUPSTQT-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
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- MAGFQRLKWCCTQJ-UHFFFAOYSA-M 4-ethenylbenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-M 0.000 description 2
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
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- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 2
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- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
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- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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- BGEVROQFKHXUQA-UHFFFAOYSA-N 71012-25-4 Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1C1=CC=CC=C1N2 BGEVROQFKHXUQA-UHFFFAOYSA-N 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
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- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
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- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
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- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- 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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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention relates to a compositionAnd the application thereof, wherein the composition is composed of a compound shown as a formula (I) and a compound shown as a formula (II). The carbazole derivative containing the arylamine group has good charge injection capability when being used as a first main body, and can effectively adjust an exciton composite interface of a light-emitting layer through structure adjustment; the formula (II) is a derivative containing indolocarbazole groups, has good hole transmission capability, and can effectively improve the hole injection capability when being used as a second main body, so that the voltage is reduced; when the two are used in combination, effective injection of charges can be realized through synergistic effect, and effective transfer of energy to dye can be realized, so that the current efficiency of the device is effectively improved.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent material composition and application thereof.
Background
In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them well suited for fabrication on flexible substrates, allowing for the design and production of aesthetically pleasing and crunchy optoelectronic products, with unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include Organic Light Emitting Diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLEDs have been developed particularly rapidly, and have been commercially successful in the field of information display.
The core of the OLED device is a film structure containing various organic functional materials. Common functionalized organic materials are: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like. When electricity is applied, electrons and holes are injected, transported to the light emitting region, and recombined therein, respectively, thereby generating excitons and emitting light.
People have developed various organic materials, and the organic materials are combined with continuously developed device structures, so that the carrier mobility can be improved, the carrier balance can be regulated and controlled, the electroluminescent efficiency can be broken through, and the attenuation of the device can be delayed. For quantum mechanical reasons, common fluorescent emitters mainly utilize singlet excitons generated when electrons and holes are combined to emit light, and are still widely applied to various OLED products. Some metal complexes, such as iridium complexes, can emit light using both triplet excitons and singlet excitons, which are called phosphorescent emitters, and the energy conversion efficiency can be increased by up to four times as compared with conventional fluorescent emitters. The Thermally Activated Delayed Fluorescence (TADF) technology can still effectively utilize triplet excitons to achieve higher luminous efficiency without using a metal complex by promoting the conversion of triplet excitons to singlet excitons. The Thermal Activated Sensitized Fluorescence (TASF) technology employs a material with TADF properties to sensitize the luminophores by means of energy transfer, and also can achieve high luminous efficiency.
As OLED products gradually enter the market, there are increasingly higher requirements for the performance of such products. The currently used OLED materials and device structures cannot completely solve the problems of OLED product efficiency, service life, cost and the like.
Therefore, there is a need in the art to develop an organic electroluminescent material that can improve the luminous efficiency of the device, reduce the driving voltage, and prolong the lifetime. The host material of the light emitting layer is an important light emitting auxiliary material, and can directly influence the device performance by effectively improving the injection and transmission of charges and adjusting an exciton recombination region, so that people pay attention to the light emitting auxiliary material.
Disclosure of Invention
Problems to be solved by the invention
From the initial improvement of luminous efficiency or the reduction of driving voltage to the desire of today, both, the demand for OLED product performance is increasing. In view of this, the present invention provides a kind of composition for organic electroluminescent devices to meet the demand of people for increasing the photoelectric properties of OLED devices.
The invention aims to provide a composition which can effectively reduce the driving voltage and improve the luminous efficiency of an organic electroluminescent device when being applied to the organic electroluminescent device as a main material of a luminous layer.
Another object of the present invention is to provide the use of the above composition as a functional material in an organic electronic device.
It is still another object of the present invention to provide an organic electroluminescent device having a light-emitting functional layer containing the above composition.
Means for solving the problems
As a result of intensive studies, the inventors have found that the above-mentioned problems can be solved by using two types of compounds having specific structures as host materials for a light-emitting layer at the same time, and an OLED having improved light-emitting efficiency, reduced driving voltage, and prolonged life as compared with the prior art can be obtained.
Specifically, one aspect of the present invention provides a composition characterized in that,
comprising a compound represented by the following formula (I) and a compound represented by the following formula (II),
wherein, L is selected from one of single bond, substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted C3-C30 heteroarylene;
a is selected from one of single bond, substituted or unsubstituted C6-C60 arylene and substituted or unsubstituted C3-C60 heteroarylene;
X 1 ～X 7 each independently selected from CR 1 Or N, R 1 Each independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, R 1 Optionally fused to an aromatic or heteroaromatic ring in which it is present;
Ar 1 is a substituted or unsubstituted C3-C30 heteroaryl; preferably, ar 1 Is a substituted or unsubstituted C3-C30 electron deficient heteroaryl;
Ar 2 、Ar 3 each independently selected from one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C5-C30 heteroaryl; (ii) a
Ar 4 、Ar 5 Each independently selected from one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamino and substituted or unsubstituted C3-C30 heteroarylamino;
when the above groups have a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1 to C20 chain alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 silyl, substituted or unsubstituted C6 to C60 arylamino, substituted or unsubstituted C3 to C60 heteroarylamino, substituted or unsubstituted C6 to C60 aryl, and substituted or unsubstituted C3 to C60 heteroaryl.
The specific reason why the above-mentioned composition of the present invention is excellent as a material for a light-emitting layer is not clear, and it is presumed that the following reasons may be: the composition simultaneously contains the compound shown in the formula (I) and the compound shown in the formula (II), the indolocarbazole with a shallow HOMO energy level is introduced, the transmission of holes in a light-emitting layer is macroscopically regulated and controlled, and meanwhile, the two compounds can balance electrons and holes and improve the exciton recombination rate, so that the composition is finally shown to be used as a device of a light-emitting layer material, compared with the prior art, the efficiency is improved, the service life is prolonged, and the driving voltage is also obviously reduced. It is to be noted that the inventors have found that when one of the compound represented by the formula (I) and the compound represented by the formula (II) is used alone as a light-emitting layer material, the device performance obtained is significantly inferior to that obtained when both are used in combination, and therefore, it is considered that there is a synergistic effect between the two.
It is to be noted that the indolocarbazole in formula (II) must be fused in such a manner that the side at position 23 of the indole is fused to the side at position 45 of the carbazole and the nitrogen atom is on the outside, i.e., the core portion of formula (II) must be indolo [2,3-c ]]Carbazole, an isomer thereof, does not achieve the above technical effects of the present invention. This may be due to the fact that the change in the HOMO energy level affects the transport of holes inside the light emitting layer. In addition, the parent nucleus part in the formula (I) is other than L 1 Compared with a compound connected with a carboline group containing nitrogen, the connected carbazole group has better hole transmission performance and can realize better service life performance of the device.
The term "electron-deficient heteroaryl" as used herein refers to a group in which the electron cloud density on the benzene ring is reduced by substituting the hydrogen on the benzene ring with the group, and usually, the Hammett value of such a group is more than 0.6. The Hammett value is a representation of the charge affinity for a particular group and is a measure of the electron withdrawing group (positive Hammett value) or electron donating group (negative Hammett value). Hammett's equation is described In more detail In Thomas H.Lowry and Katheleen Schueller Richardson, "mechanics and Theory In Organic Chemistry', new York,1987, pages 143-151, which is incorporated herein by reference. Such groups may be listed but are not limited to: triazinyl, pyrimidinyl, benzopyrimidinyl, benzopyridyl, naphthyridinyl, phenanthridinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, pyridazinyl, and alkyl-or aryl-substituted ones of the foregoing.
In the present invention, the expression of Ca to Cb means that the group has carbon atoms of a to b, and the carbon atoms do not generally include the carbon atoms of the substituents unless otherwise specified. In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, such as the expression of "hydrogen", and also includes the concept of chemically identical "deuterium" and "tritium". "independently" means that the subject may be the same or different from each other when there are a plurality of subjects.
In the structural formula R 1 Etc., indicate that the substitution position may be any possible position on the ring. The expressions for other substituted bonds in the structural formulae are all similar in meaning.
In the present invention, unless otherwise specified, a substituent is not condensed with a group in which it is present.
In the present specification, the C1-C20 linear alkyl group is preferably a C1-C10 linear alkyl group, more preferably a C1-C6 linear alkyl group, and examples thereof include: methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-pentyl, n-heptyl, n-nonyl, n-decyl, and the like.
In the present specification, the cycloalkyl group of C3 to C20 is preferably a C3 to C10 cycloalkyl group, and more preferably a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclodecyl group, adamantyl group or the like.
In the present specification, examples of the C1-C10 alkoxy group include groups in which the above-mentioned alkyl group is bonded to-O-, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, and the like, and among them, methoxy, ethoxy, propoxy, and more preferably methoxy are preferred.
In this specification, C6-C30 aryl includes C6-C30 monocyclic aryl or C10-C30 fused ring aryl, wherein monocyclic aryl means that the aromatic ring is present as a single ring, absent a fusion, including but not limited to phenyl, biphenyl, or terphenyl; a fused ring aryl refers to a structure in which at least two aromatic rings are fused, including, but not limited to, naphthyl, anthryl, phenanthryl, fluorenyl, and the like.
In this specification, a C3-C30 heteroaryl group includes a C3-C30 monocyclic heteroaryl group or a C6-C30 fused ring heteroaryl group, wherein monocyclic heteroaryl group means that the heteroaryl ring is present as a single ring, absent fusion, including but not limited to furan, thiophene, pyridine, pyrimidine, triazine, or a group of at least two joined together, and the like; fused heteroaryl refers to a fused ring aryl group containing a heteroatom, including but not limited to a dibenzofuran group, a dibenzothiophene group, or a carbazole group, and the like.
The substituted or unsubstituted C6-C30 aryl group, preferably C6-C30 aryl group, of the invention is preferably phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and derivatives thereof, fluoranthryl, triphenylene, pyrenyl, perylenyl, perylene, or the like,
Radicals in the radical and tetracenyl. The biphenyl groups include 2-biphenyl, 3-biphenyl, 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl group, 2-naphthyl group; the anthracene group comprises a 1-anthracene group, a 2-anthracene group and a 9-anthracene group; the fluorenyl group comprises 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group and 9-fluorenyl group; the fluorenyl derivative comprises 9,9-dimethylfluorene, 9,9-spirobifluorene and benzofluorene; the describedThe pyrenyl group comprises 1-pyrenyl group, 2-pyrenyl group and 4-pyrenyl group; the tetracenyl includes 1-tetracenyl, 2-tetracenyl and 9-tetracenyl.
The substituted or unsubstituted C3-C30 heteroaryl group, preferably the heteroaryl group is furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, indolocarbazole.
In the present specification, arylamino means-NH 2 Two or one H of the group is substituted with an aryl group, wherein the aryl group includes monocyclic aryl groups and fused ring aryl groups. The site of attachment of the arylamino group in the present invention may be on N or a substituent on N, in other words, the arylamino group may be attached to the rest of the molecule through N or a substituent. Examples of the C6-C30 arylamino group include: phenylamino, methylphenylamino, naphthylamino, anthrylamino, phenanthrylamino, biphenylamino and the like.
In the present specification, examples of the C3-C30 heteroarylamino group include: pyridylamino, pyrimidylamino, dibenzofuranylamino and the like.
In this specification, arylene is to be understood as meaning a group which differs from the corresponding aryl by the removal of one more hydrogen than the corresponding aryl. Heteroarylene groups are to be construed in scope as referring to the corresponding heteroaryl group except that one more hydrogen has been removed from the corresponding heteroaryl group.
In the present specification, the "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from the group.
In the present invention, X is preferred 1 ～X 7 Each independently selected from CR 1 ，R 1 Each independentlySelected from hydrogen, substituted or unsubstituted C1 to C20; one of a chain alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C1-C20 silyl group, a substituted or unsubstituted C6-C30 arylamino group, and a substituted or unsubstituted C6-C30 aryl group; more preferably, said R 1 Each independently selected from hydrogen.
By adding R 1 The above-mentioned group is advantageous in that the driving voltage of an organic electroluminescent device using the composition can be further reduced as compared with the case where other groups are selected.
In the present invention, preferably A is a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C3 to C30 heteroarylene group;
more preferably, a is phenylene, naphthylene, biphenylene, dibenzofuranylene, or dibenzothiophenylene.
In the present invention, ar is preferred 1 Is a substituted or unsubstituted C3-C30 electron-deficient heteroaryl group containing at least two N;
more preferably Ar is mentioned 1 One selected from the following substituted or unsubstituted groups: pyrimidinyl, triazinyl, quinazolinyl, quinoxalinyl.
In the present invention, ar is preferred 1 Selected from the following substituted or unsubstituted groups:
by introducing Ar 1 By providing such a group, the degree of planarization of the compound represented by formula (I) is improved as compared with the selection of other groups, which is advantageous in further reducing the driving voltage of an organic electroluminescent device using the above composition.
In the present invention, ar is preferred 4 And Ar 5 Each independently selected from one of substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;
more preferably Ar 4 And Ar 5 Each independently selected from: phenyl, biphenyl, terphenyl, naphthyl, triphenylene, pyrenyl, phenanthreneA fluoranthenyl group, a fluorenyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, and combinations thereof.
By introducing Ar 4 And Ar 5 By providing the above group, the planarization degree of the compound represented by the formula (II) is improved as compared with selecting other groups, which is advantageous for further reducing the driving voltage of the organic electroluminescent device using the above composition. Meanwhile, the group has good thermal stability, so that the group has better stability when being used for an organic electroluminescent device.
In the present invention, it is preferable that the compound represented by the formula (I) is selected from the following compounds:
in the present invention, it is preferable that the compound represented by the formula (II) is selected from the following compounds:
another aspect of the present invention relates to the use of the above composition in an organic electroluminescent device. The composition of the present invention can be applied not only to organic electroluminescent devices but also to other types of organic electronic devices including organic field effect transistors, organic thin film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners or electronic paper. The composition is preferably used as a host material of a light-emitting layer in an organic electroluminescent device.
In a further aspect, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layers contain the above-described composition of the present invention.
In the organic electroluminescent device of the present invention, in the above composition of the present invention contained in the light-emitting functional layer, the weight ratio of the compound represented by formula (I) to the compound represented by formula (II) is preferably 1: 99 to 99: 1, more preferably 30: 70 to 70: 30.
Effects of the invention
The specific reason why the compound of the present invention has excellent properties is not clear, and it is presumed that the following reasons may be mentioned:
the triarylamine compound is a common hole transport material type by virtue of good hole transport capability, and meanwhile, a good amorphous film can be prepared by virtue of a special tetrahedral structure, so that the triarylamine compound shows good film-forming property when being used as an organic electroluminescent device material; according to the compound 1, arylamine groups are introduced into carbazole derivatives, and the performance is improved through specific modification; the main reasons are the following: 1. due to the introduction of the arylamine, the compound maintains good hole transmission capability, the balance of a composite region is realized, and the efficiency can be effectively improved. 2. The introduction of the aromatic amine group improves the accumulation density of molecules and forms a stable film structure;
furthermore, the compound 2 preferably selects an indolocarbazole derivative, the group has good plane rigidity, and the accumulation density of the material is improved, and meanwhile, the group still has good hole transmission capability and a proper HOMO energy level, so that the hole injection capability is effectively improved, and the voltage of a device is improved; when the compound is matched and combined with the compound 1 for use, the stability of the device can be further improved.
In addition, the preparation process of the compound is simple and feasible, the raw materials are easy to obtain, and the compound is suitable for mass production and amplification.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Device embodiments
Next, the organic electroluminescent device will be explained in detail.
Specifically, another technical scheme of the invention provides an organic electroluminescent device, which comprises a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer which are sequentially formed on the substrate; the light-emitting functional layer comprises at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer and an electron transport layer, wherein the light-emitting layer contains at least one of the compounds.
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material serving as the first electrode on the substrate. When the first electrode is used as an anode, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) may be used 2 ) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multi-layer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL); wherein the HIL is located between the anode and the HTL and the EBL is located between the HTL and the light emitting layer.
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3,4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-51; or any combination thereof.
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-51 described above, or one or more compounds of HI-1-HI-3 described below; one or more of the compounds HT-1 to HT-51 may also be used to dope one or more of the compounds HI-1-HI-3 described below.
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, or the like. The plurality of monochromatic light emitting layers of different colors may be arranged in a planar manner according to a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, or the like at the same time.
According to different technologies, the material of the light-emitting layer can be different materials such as a fluorescent electroluminescent material, a phosphorescent electroluminescent material, a thermal activation delayed fluorescence luminescent material and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These different luminescent materials, which are technically classified, may emit light of the same color, but also of different colors.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer can be selected from, but is not limited to, one or more of GPD-1 to GPD-47 listed below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light emitting layer thereof may be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.
In one aspect of the invention, the light-emitting layer employs phosphorescent electroluminescent technology. The phosphorescent dopant of the light-emitting layer can be selected from, but is not limited to, one or more of YPD-1-YPD-11 listed below.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-73 listed below.
In one aspect of the invention, a Hole Blocking Layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more compounds of ET-1 to ET-73 or one or more compounds of PH-1 to PH-46; mixtures of one or more compounds from ET-1 to ET-73 with one or more compounds from PH-1 to PH-46 may also be used, but are not limited thereto.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following: liQ, liF, naCl, csF, li 2 O、Cs 2 CO 3 BaO, na, yb, li or Ca. The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Specifically, the following synthesis examples of the present invention exemplarily provide specific synthesis methods of representative compounds, and in addition, those skilled in the art can synthesize the compounds by known methods.
Synthesis example 1: synthesis of Compound P1
S1 (30 mmol), S2 (30 mmol), potassium carbonate (45 mmol) and DMF (200 ml) were added to a reaction flask, heated to reflux for 3h, TLC monitored reaction completion, reaction solution was poured into water and filtered, filter cake toluene recrystallized to give M1 (25 mmol) as a white solid. Subsequently, M1 (25 mmol), S3 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml) and water (40 ml) were put into a 500ml three-necked flask under nitrogen flow, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, followed by separation into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated over anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification by column chromatography gave a yellow solid. Further, the obtained yellow solid was recrystallized from methylene chloride and ethanol to obtain a P1 compound. M/Z theoretical value: 614.25; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 615.25.
synthesis example 2: synthesis of Compound P5
Under a nitrogen stream, the above M1 (25 mmol), S4 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml) and water (40 ml) were charged in a 500ml three-necked flask, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, followed by separation into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification by column chromatography gave a yellow solid. Further, the obtained yellow solid was recrystallized from methylene chloride and ethanol to obtain a P5 compound.
M/Z theoretical value: 740.29; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 740.25.
synthesis example 3: synthesis of Compound P16
Under a nitrogen stream, the above M1 (25 mmol), S5 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml) and water (40 ml) were charged in a 500ml three-necked flask, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, to separate into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated over anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification was performed by column chromatography to obtain a yellow solid. Further, the obtained yellow solid was recrystallized from methylene chloride and ethanol to obtain a P16 compound. M/Z theoretical value: 704.26; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 705.25.
synthesis example 4: synthesis of Compound P19
Under a nitrogen stream, the above M1 (25 mmol), S6 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml) and water (40 ml) were charged in a 500ml three-necked flask, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, followed by separation into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification by column chromatography gave a yellow solid. Further, the obtained yellow solid was recrystallized from methylene chloride and ethanol to obtain a P19 compound. M/Z theoretical value: 615.24; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 616.24.
synthesis example 5: synthesis of Compound P39
S1 (30 mmol), S7 (30 mmol), potassium carbonate (45 mmol) and DMF (200 ml) were added to a reaction flask, heated to reflux for 3h, TLC monitored completion of the reaction, poured into water and filtered, and the filter cake recrystallized from toluene to give M2 (23 mmol) as a white solid.
Subsequently, under a nitrogen stream, intermediate M2 (25 mmol), S8 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml), and water (40 ml) were charged into a 500ml three-necked flask, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, to separate into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification was performed by column chromatography to obtain a yellow solid. Further, the crude product was recrystallized from dichloromethane and ethanol to obtain a P39 compound.
M/Z theoretical value: 730.31; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 731.30.
synthesis example 6: synthesis of Compound P46
Under a nitrogen stream, intermediate M2 (25 mmol), S4 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml), and water (40 ml) were added to a 500ml three-necked flask, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, to separate into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification was performed by column chromatography to obtain a yellow solid. Further, the obtained yellow solid was recrystallized from methylene chloride and ethanol to obtain a P46 compound. M/Z theoretical value: 740.29; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 741.30.
synthesis example 7: synthesis of Compound P55
S1 (30 mmol), S9 (30 mmol), potassium carbonate (45 mmol) and DMF (200 ml) were added to a reaction flask, heated to reflux for 3h, TLC monitored reaction completion, reaction solution was poured into water and filtered, filter cake toluene recrystallized to give M3 (26 mmol) as a white solid.
Subsequently, the intermediate M3 (25 mmol), S4 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml) and water (40 ml) were added to a 500ml three-necked flask under a nitrogen stream, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, followed by separation into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification by column chromatography gave a yellow solid. Further, the crude product was recrystallized from dichloromethane and ethanol to give a P55 compound.
M/Z theoretical value: 767.30; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 768.30.
synthesis example 8: synthesis of Compound P67
S1 (30 mmol), S10 (30 mmol), potassium carbonate (45 mmol) and DMF (200 ml) were added to a reaction flask, heated to reflux for 3h, TLC monitored reaction completion, reaction solution was poured into water and filtered, filter cake toluene recrystallized to give M4 (26 mmol) as a white solid.
Subsequently, the intermediate M4 (25 mmol), S11 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml) and water (40 ml) were added to a 500ml three-necked flask under a nitrogen stream, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, followed by separation into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification was performed by column chromatography to obtain a yellow solid. Further, the crude product was recrystallized from dichloromethane and ethanol to obtain the P67 compound. M/Z theoretical value: 886.35; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 887.35.
synthesis example 9: synthesis of Compound P73
S1 (30 mmol), S12 (30 mmol), potassium carbonate (45 mmol) and DMF (200 ml) were added to a reaction flask, heated to reflux for 3h, TLC monitored reaction completion, reaction solution was poured into water and filtered, filter cake toluene recrystallized to give M5 (24 mmol) as a white solid.
Subsequently, the intermediate M5 (25 mmol), S13 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml) and water (40 ml) were added to a 500ml three-necked flask under a nitrogen stream, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, to separate into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification was performed by column chromatography to obtain a yellow solid. Further, the crude product was recrystallized from dichloromethane and ethanol to obtain the P73 compound.
M/Z theoretical value: 690.28; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 691.25.
synthesis example 10: synthesis of Compound P108
S14 (30 mmol), S15 (30 mmol), potassium carbonate (45 mmol) and DMF (200 ml) were added to a reaction flask, heated to reflux for 3h, TLC monitored reaction completion, reaction solution was poured into water and filtered, filter cake toluene recrystallized to give M6 (24 mmol) as a white solid. Subsequently, under a nitrogen stream, intermediate M6 (25 mmol), S16 (25 mmol), tetrakis (triphenylphosphine) palladium (0.25 mmol), potassium carbonate (38 mmol), 1,4-dioxane (200 ml), and water (40 ml) were charged into a 500ml three-necked flask, followed by stirring at 110 ℃ for 3 hours. After cooling to room temperature, 150ml of ethyl acetate was added thereto and stirred, followed by separation into an organic layer and an aqueous layer. The organic layer was washed with water 3 times, and the resulting organic layer was dehydrated with anhydrous sodium sulfate, filtered to remove sodium sulfate, and the solvent was distilled off under reduced pressure. Thereafter, purification was performed by column chromatography to obtain a yellow solid. Further, the crude product was recrystallized from dichloromethane and ethanol to obtain the P108 compound. M/Z theoretical value: 732.26; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 733.25.
synthesis example 11: synthesis of Compound C2
S17 (30 mmol), S18 (60 mmol), cuI (6 mmol), 1, 10-phenanthroline (6 mmol) and K2CO3 (90 mmol 1) were charged to a 250mL reaction flask, to which was added 100mL of DMF and stirred at reflux under a nitrogen atmosphere for 24h. When the reaction was completed, the resultant was treated with distilled water to precipitate a solid, and then filtered. The crude product was filtered through silica gel to give a white solid, giving compound C2.M/Z theoretical value: 560.23; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 561.24.
synthesis example 12: synthesis of Compound C5
S17 (30 mmol), S19 (30 mmol), cuI (6 mmol), 1, 10-phenanthroline (6 mmol), and K2CO3 (90 mmol 1) were charged to a 250mL reaction flask, to which was added 100mL of DMF, and stirred at reflux under a nitrogen atmosphere for 24h. When the reaction was completed, the resultant was treated with distilled water to precipitate a solid, and then filtered. The crude product was filtered through silica gel to give a white solid, yielding intermediate M7.
M7 (30 mmol), S20 (30 mmol), cuI (6 mmol), 1, 10-phenanthroline (6 mmol), and K2CO3 (90 mmol 1) were charged to a 250mL reaction flask, to which was added 100mL of DMF, and stirred at reflux under a nitrogen atmosphere for 24h. When the reaction was completed, the resultant was treated with distilled water to precipitate a solid, which was then filtered. The crude product was filtered through silica gel to give compound C5.M/Z theoretical value: 560.23; ZAB-HS type mass spectrometer (manufactured by Micromass, UK) [ M + H ] found: 561.23.
example 1
The embodiment provides an organic electroluminescent device, which is specifically prepared by the following steps:
the glass plate coated with the ITO transparent conductive layer (as anode) was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 1 × 10 -5 Pa, vacuum evaporating 10nm HT-4 on the anode layer film: HI-3 (97/3,w/w) mixture as hole injection layer; 60nm of compound HT-4 as hole transport layer; 60nm of compound HT48 as an electron blocking layer;
a light-emitting layer of the device is vacuum-evaporated on the electron blocking layer, the light-emitting layer comprises a main material and a dye material, the first main material P1 and the second main material C2 are doped according to the proportion of 1: 1 by utilizing a multi-source co-evaporation method, the dye RPD-8 is doped according to the proportion of 3wt%, and the total film thickness of evaporation is 40nm;
and (3) vacuum evaporating a 25nm compound ET-69 on the light-emitting layer: ET-57 (50/50, w/w) mixture as electron transport layer; liF with the thickness of 0.5nm is taken as an electron injection layer, and metal aluminum with the thickness of 150nm is taken as a cathode of the device;
the organic electroluminescent devices provided in examples 2 to 19 and comparative examples 1 to 5 were fabricated in the same manner as in example 1, except that the host materials of the light-emitting layer were replaced with the compounds shown in table 1 below. Examples 20 to 21 provide organic electroluminescent devices manufactured in the same manner as in example 1, except that the doping ratios of the host materials of the light-emitting layer were changed to the ratios shown in table 1 below.
The light-emitting layer host materials of comparative examples 1 to 5 were selected from compounds R1 to R3 having the following structures:
performance test
(1) The organic electroluminescent devices prepared in examples and comparative examples were measured for driving voltage and current efficiency and lifetime of the devices at the same brightness. Specifically, the luminance of the organic electroluminescent device was measured to reach 3000cd/m by raising the voltage at a rate of 0.1V per second 2 The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency;
(2) The life test of LT97 is as follows: using 60mA/cm 2 The time for which the luminance of the organic electroluminescent device was decreased to 97% was measured with the life of example 1 as a standard while maintaining a constant current. The test results are shown in Table 1.
Table 1:
as can be seen from the data in Table 1, when the compound of the present invention is used in the host material of the light-emitting layer of an organic electroluminescent device, the luminance of the device reaches 3000cd/m 2 When the voltage is lower than 4.1V, the current efficiency is higher than 20cd/A and 60mA/cm 2 Compared with the comparative example, the LT97 is obviously improved, can effectively reduce the driving voltage and improve the current efficiency, and is a luminescent layer main body material with good performance.
It can be seen from the results of comparing the devices of examples 1 to 4 and comparative examples 1 to 2 that when the combination of the compound represented by formula (I) and the compound represented by formula (II) is used as the host material of the light-emitting layer, the voltage of the device can be effectively reduced, the efficiency of the device can be improved, and the lifetime of the device can be significantly improved, because the compound 1 and the compound 2 are respectively p-type and n-type structural materials, which is beneficial to the injection of electrons and holes, and the bipolar characteristic of the two when doped for use can greatly improve the recombination region of carriers, thereby improving the performance of the device. Meanwhile, there is a tendency for the lifetimes of examples 1-3 to gradually increase, which may be associated with a gradual increase in the hole transport properties of the host material.
It can be seen from the results of comparing the devices in example 9 and comparative example 3 that, when the first compound is P67, the lifetime of the first compound is significantly improved compared to that of comparative example 3, which is that P67 is substituted by amino groups added to the comparative compound R1, and the strong hole transport capability of the amino groups makes the exciton recombination interface more biased to the electron transport layer side, so as to be far away from the electron blocking layer and the light emitting layer interface, thereby effectively improving the stability of the device.
It can be seen from the device results of comparative example 11 and comparative example 4 that compared with the bicarbazole derivative of the compound R2, the selected indolocarbazole derivative of the present invention can effectively reduce the voltage, which is the reason that the energy barrier at the hole side of the device is effectively reduced due to the more matched HOMO energy level, so that the hole injection is more convenient.
It can be seen from the device results of comparing example 1 and examples 17-18 that as the proportion of the second host material compound C2 increases, the lifetime of the device gradually improves, but the efficiency slightly decreases, which may be due to the fact that the charge transport performance of the host material changes correspondingly and the exciton recombination zone shifts correspondingly through the change of the doping proportion, and as the exciton recombination zone gradually moves away from the interface, the stability of the device improves, but the exciton concentration decreases, the efficiency decreases, and therefore the device performance can be optimally improved by adjusting the compound doping proportion.
In conclusion, the compound disclosed by the invention is specially designed, has appropriate comprehensive performance, and is expected to be well applied in actual production. The present invention is illustrated by the above examples of the compounds of the present invention and their application in OLED devices, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention has to be implemented by means of the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The experimental data show that when the organic material combination is used as the main material of the luminescent layer of the organic electroluminescent device, the organic material combination is obviously improved compared with the prior art, is an organic luminescent functional material with good performance, and has wide application prospect.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (11)
1. A composition characterized in that it comprises, in a first aspect,
comprising a compound represented by the following formula (I) and a compound represented by the following formula (II),
wherein, L is selected from one of single bond, substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted C3-C30 heteroarylene;
a is selected from one of single bond, substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted C3-C30 heteroarylene;
X 1 ～X 7 each independently selected from CR 1 Or N, R 1 Each independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstitutedOne of C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, R 1 Optionally fused to an aromatic or heteroaromatic ring in which it is present;
Ar 1 is a substituted or unsubstituted C3-C30 heteroaryl; preferably, ar 1 Is a substituted or unsubstituted C3-C30 electron-deficient heteroaryl;
Ar 2 、Ar 3 each independently selected from substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C5-C30 heteroaryl;
Ar 4 、Ar 5 each independently selected from one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamino and substituted or unsubstituted C3-C30 heteroarylamino;
when the above groups have a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1 to C20 chain alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C1 to C20 alkoxy, substituted or unsubstituted C1 to C20 silyl, substituted or unsubstituted C6 to C60 arylamino, substituted or unsubstituted C3 to C60 heteroarylamino, substituted or unsubstituted C6 to C60 aryl, and substituted or unsubstituted C3 to C60 heteroaryl.
2. The composition of claim 1,
said X 1 ～X 7 Each independently selected from CR 1 ，R 1 Each independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C30 arylamino, and substituted or unsubstituted C6-C30 aryl;
preferably, said R is 1 Each independently selected from hydrogen.
3. The composition of claim 1,
a is substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C3-C30 heteroarylene;
preferably, a is phenylene, naphthylene, biphenylene, dibenzofuranylene, or dibenzothiophenyl.
4. The composition of claim 1,
ar is 1 Is a substituted or unsubstituted C3-C30 electron-deficient heteroaryl group containing at least two N;
preferably, said Ar 1 One selected from the following substituted or unsubstituted groups: pyrimidinyl, triazinyl, quinazolinyl, quinoxalinyl.
5. The composition of claim 1,
ar is 1 Selected from the following substituted or unsubstituted groups:
6. the composition of claim 1,
ar is 4 And Ar 5 Each independently selected from one of substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;
preferably, ar is 4 And Ar 5 Each independently selected from: phenyl, biphenyl, terphenyl, naphthyl, triphenylene, pyrenyl, phenanthrenyl, fluoranthenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, and combinations thereof.
7. The composition of claim 1,
the compound shown in the formula (I) is selected from the following compounds:
8. the composition of claim 1,
the compound shown in the formula (II) is selected from the following compounds:
9. use of the composition according to any one of claims 1 to 8 as a functional material in an organic electronic device comprising an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner or electronic paper;
the use of the composition as a host material for the light-emitting layer in an organic electroluminescent device is preferred.
10. An organic electroluminescent device characterized in that,
comprising a first electrode, a second electrode and one or more light-emitting functional layers interposed between said first and second electrodes, said light-emitting functional layers containing the composition according to claims 1 to 8.
11. The organic electroluminescent device according to claim 10,
the composition according to claims 1 to 8, wherein the weight ratio of the compound represented by formula (I) to the compound represented by formula (II) is 1: 99 to 99: 1;
preferably, the weight ratio of the compound of formula (I) to the compound of formula (II) is from 30: 70 to 70: 30.
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