CN115636821A - Electron transport material and preparation method and application thereof - Google Patents
Electron transport material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 7
- 125000006818 (C3-C60) cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims abstract description 3
- 125000006761 (C6-C60) arylene group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004306 triazinyl group Chemical group 0.000 claims description 4
- 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 3
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 125000004653 anthracenylene group Chemical group 0.000 claims description 3
- 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 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 3
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 claims description 3
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 3
- 125000005567 fluorenylene group Chemical group 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000001041 indolyl group Chemical group 0.000 claims description 3
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000004957 naphthylene group Chemical group 0.000 claims description 3
- 125000002971 oxazolyl group Chemical group 0.000 claims description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- 125000005560 phenanthrenylene group Chemical group 0.000 claims description 3
- 125000005561 phenanthryl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 3
- 125000001725 pyrenyl group Chemical group 0.000 claims description 3
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 3
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 3
- 125000005493 quinolyl group Chemical group 0.000 claims description 3
- 125000006836 terphenylene group Chemical group 0.000 claims description 3
- 125000000335 thiazolyl group Chemical group 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- -1 N-phenylcarbazolyl Chemical group 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 40
- 238000012360 testing method Methods 0.000 description 17
- 238000000921 elemental analysis Methods 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 12
- 238000004949 mass spectrometry Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 150000003413 spiro compounds Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- PFWJFKBTIBAASX-UHFFFAOYSA-N 9h-indeno[2,1-b]pyridine Chemical group C1=CN=C2CC3=CC=CC=C3C2=C1 PFWJFKBTIBAASX-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an electron transport material, a preparation method and application thereof, wherein the electron transport material has a structure shown as a formula I, wherein L 1 And L 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C3-C60 cycloalkyl group, and a substituted or unsubstituted C2-C60 heterocyclic group; ar (Ar) 1 And Ar 2 Selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heterocyclic radical,At least one substituted or unsubstituted C3-C60 cycloalkyl. The electron transport material has excellent charge transfer capacity and good thermal stability, and can effectively improve the luminescence property and the service life of a device when being used as the electron transport material of an electroluminescent device.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an electron transport material and a preparation method and application thereof.
Background
Organic Electroluminescence (EL) is an electric energy excited organic material to emit light, and an Organic Light Emitting Diode (OLED) is a device for generating electroluminescence using a multi-layered organic thin film structure, is simple to manufacture, requires only a very low driving voltage, and has excellent display characteristics and qualities such as self-luminescence, a wide viewing angle, high efficiency, a wide color gamut, and flexible display, compared to an LCD.
The OLED functional material with high performance is selected and reasonably matched, so that the comprehensive characteristics of high efficiency, long service life and low voltage of the device are exerted. Materials constituting the organic material layer, such as a hole transport material, a light emitting material, an electron transport material, and the like, should have characteristics of having fluorescence with higher efficiency in a visible light region, having higher conductivity, and exhibiting good semiconductor characteristics; has good film forming property, and the formed film has better uniformity and the like.
CN109942552A discloses a compound comprising triazinyl, fluorenyl and heterofluorenyl groups, in particular, the compound disclosed therein is suitable as a layer material of an electronic device, and the compound disclosed therein is as an organic semiconductor layer, an organic electronic device comprising at least one of said organic semiconductor layers and a method of manufacturing said organic electronic device.
CN106103441B discloses a spiro compound having an azafluorene ring structure, a light-emitting material and an organic electroluminescent device, and discloses the spiro compound as a material for a high-efficiency organic electroluminescent device to provide a compound emitting fluorescence and delayed fluorescence, and further provides an organic electroluminescent device, a high-efficiency, high-luminance organic electroluminescent device using the compound. The organic electroluminescent device disclosed therein is an organic electroluminescent device having a pair of electrodes and at least one organic layer sandwiched therebetween, and the compound disclosed therein is used as a constituent material of at least 1 organic layer.
CN112390780A discloses an electron transport material containing nitrogen hetero-spirobifluorene, and the disclosed compound is a compound with a nitrogen hetero-spirobifluorene structure and can be used as an electron transport material in an electroluminescent device. These novel compounds provide longer device lifetimes, and an electroluminescent device and compound formulation are also disclosed.
Although the prior art discloses an electron transport material and application thereof in an OLED device, the electron transport material still has few types, and has the problems of poor thermal stability, low transport efficiency, influence on the service life of the device due to crystallization in the use process and the like, and the preparation process requirements and the use performance requirements of the device cannot be met.
In view of the above, it is a research focus in the art to develop a wider variety of electron transport materials having excellent stability and high-efficiency transport properties to meet the needs of OLEDs having low driving voltage, high efficiency, high luminance, and long lifetime.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an electron transport material, a preparation method and an application thereof, wherein the electron transport material is endowed with excellent charge transfer capacity and good thermal stability through the design of a compound parent nucleus structure and the introduction of a substituent on a specific site, and the electron transport material can be used as an electron transport material of an electroluminescent device to effectively improve the luminescence property and the service life of the device.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an electron transport material having a structure represented by formula I:
wherein L is 1 And L 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C3-C60 cycloalkyl group, and a substituted or unsubstituted C2-C60 heterocyclic group;
Ar 1 and Ar 2 At least one selected from the group consisting of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heterocyclic group, and substituted or unsubstituted C3-C60 cycloalkyl.
The term "C6-C60" as used herein refers to the number of carbon atoms in the group, and the same applies to "C3-C60" and "C2-C60".
The C6 to C60 may be C6, C7, C8, C9, C10, C12, C15, C18, C20, C22, C24, C25, C27, C29, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C57, C59, or the like.
The C3 to C60 may be C4, C5, C6, C8, C10, C12, C15, C18, C20, C22, C24, C25, C27, C29, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C57, C59, or the like.
The C2 to C60 may be C3, C4, C5, C6, C8, C10, C12, C15, C18, C20, C22, C24, C25, C27, C29, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C57, C59, etc.
The electron transport material provided by the invention is a polycyclic aromatic hydrocarbon compound containing unsaturated bonds, a parent nucleus structure which is favorable for electron transport is formed by a large conjugated system and strong electron withdrawing property of triazine, and the electron transport material has the synergistic effect of a substituent group with a conjugated effect and the parent nucleus structure, can further improve the conjugated effect of the electron transport material, enables the electron transport material to have excellent electron transport capacity, thereby effectively improving the luminous performance and the service life of a device, and reducing the driving voltage.
Preferably, the heteroatom in the heterocyclic group is selected from any one of O, N, S or Si.
In the present invention, the arylene group illustratively includes, but is not limited to: phenylene, biphenylene, terphenylene, naphthylene, anthracenylene, phenanthrenylene, fluorenylene, and the like.
The aryl group, illustratively including but not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, spirofluorenyl, or the like.
The heteroaryl group, illustratively including but not limited to: n-phenylcarbazolyl, furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, carbazolyl, acridinyl, imidazolyl, oxazolyl, thiazolyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, benzimidazolyl, quinolyl, isoquinolyl and the like.
Preferably, the arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, anthracenylene, phenanthrenylene, or fluorenylene.
Preferably, the aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl or spirofluorenyl.
Preferably, the heteroaryl group is selected from any one of N-phenylcarbazolyl, furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, carbazolyl, acridinyl, imidazolyl, oxazolyl, thiazolyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, benzimidazolyl, quinolyl or isoquinolyl.
Preferably, said L 1 And L 2 Each independently selected from a single bond and a C6-C12 arylene group (e.g., C7, C8, C9, C10, C11, etc.), with a single bond being more preferred.
Preferably, ar is 1 And Ar 2 Each independently selected from at least one of the following groups:
wherein "-" represents the linkage of the group.
Preferably, the electron transport material comprises any one or a combination of at least two of the following compounds H1-H14:
in a second aspect, the present invention provides a method for preparing the electron transport material of the first aspect, the method comprising the steps of:
will be provided with
And
L 1 、L 2 、Ar 1 and Ar 2 Each independently having the same limitations as claim 1;
and X is halogen.
Preferably, the catalyst is a palladium catalyst.
Preferably, said X is Cl.
In a third aspect, the present invention provides an OLED device, which at least includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode, which are sequentially stacked, and the material of the electron transport layer includes the electron transport material according to the first aspect.
Preferably, the hole injection layer has a thickness of 55-65nm, such as 56nm, 57nm, 58nm, 59nm, 60nm, 61nm, 62nm, 63nm, 64nm, and the like.
Preferably, the hole transport layer has a thickness of 75-85nm, such as 76nm, 77nm, 78nm, 79nm, 80nm, 81nm, 82nm, 83nm, 84nm, and the like.
Preferably, the thickness of the light-emitting layer is 25-35nm, such as 26nm, 27nm, 28nm, 29nm, 30nm, 31nm, 32nm, 33nm, 34nm, and the like.
Preferably, the thickness of the electron transport layer is 35-45nm, such as 36nm, 37nm, 38nm, 39nm, 40nm, 41nm, 42nm, 43nm, 44nm, and the like.
Preferably, the electron injection layer has a thickness of 1 to 3nm, such as 1.2nm, 1.4nm, 1.6nm, 1.8nm, 2nm, 2.2nm, 2.4nm, 2.6nm, 2.8nm, and the like.
In a fourth aspect, the present invention provides an electronic device comprising the OLED device of the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
the electron transport material has excellent charge transfer capacity and good thermal stability, can effectively improve the luminous performance and the service life of an electroluminescent device when being used as the electron transport material of the electroluminescent device, and has the current efficiency of 7.12-8.25 Cd/A, the T95 of 280-310 h and the driving voltage of 3.58-3.64V.
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 limitation of the present invention.
The starting compounds of the following examples of the present invention (including compounds A1 to A9) are commercially available.
Example 1
The present embodiment provides an electron transport material having the following structure:
the preparation method comprises the following steps:
under an argon atmosphere, 3g of intermediate A1,5g of intermediate A2,0.16mmol of palladium acetate (Pd (pph) 3 ) 4 ) 0.32mmol of tri-tert-butylphosphine, 9.6mmol of potassium carbonate (K) 2 CO 3 ) And 50mL of tetrahydrofuran, stirring at 125 ℃ for 12h, and separating and recrystallizing the solid obtained by the reaction by silica gel column chromatography to obtainTo 5.3g of the expected product, compound H1, in 66% yield.
Target product structure was tested according to mass spectrometry (HRMS):
C 63 H 40 N 4 o, calculated molecular weight: 868.32, test value: 869.04;
theoretical value of elemental analysis: c:87.07, O:1.84, N:6.45, H:4.64 of;
elemental analysis test value: c:87.13, O:1.85, N:6.34, H:4.55.
example 2
The present embodiment provides an electron transport material having the following structure:
the preparation method comprises the following steps:
3g of intermediate A3,5g of intermediate A2,0.16mmol of palladium acetate, 0.32mmol of tri-tert-butylphosphine, 9.6mmol of potassium carbonate and 50mL of tetrahydrofuran are mixed under an argon atmosphere, stirred at 125 ℃ for 12H, and the solid obtained from the reaction is purified by column chromatography on silica gel and recrystallization to give 5.1g of the target compound H2 in 63% yield.
The target product structure was tested according to mass spectrometry (HRMS):
C 76 H 50 N 4 calculated molecular weight value: 1018.4, test value: 1019.26;
theoretical value of elemental analysis: c:89.56, N:5.50, H:4.94;
elemental analysis test value: c:90.02, N:4.91, H:4.84.
example 3
The embodiment provides an electron transport material, which has the following structure:
the preparation method comprises the following steps:
3g of intermediate A4,5g of intermediate A2,0.16mmol of palladium acetate, 0.32mmol of tri-tert-butylphosphine, 9.6mmol of potassium carbonate and 50mL of tetrahydrofuran are mixed under an argon atmosphere, stirred at 125 ℃ for 12H, and the solid obtained from the reaction is purified by silica gel column chromatography and recrystallization to give 4.2g of the target compound H3 in 53% yield.
Target product structure was tested according to mass spectrometry (HRMS):
C 69 H 46 N 4 calculated molecular weight value: 930.37, test value: 931.15;
theoretical value of elemental analysis: c:89.38, N:6.02, H:5.07;
elemental analysis test value: c:89.00, N:6.45, H:5.13.
example 4
The embodiment provides an electron transport material, which has the following structure:
the preparation method comprises the following steps:
3g of intermediate A5,4g of intermediate A6,0.16mmol of palladium acetate, 0.32mmol of tri-tert-butylphosphine, 9.6mmol of potassium carbonate and 50mL of tetrahydrofuran are mixed under argon, stirred at 25 ℃ for 12H, and the solid obtained from the reaction is purified by chromatographic separation on a silica gel column and recrystallization to give 4.0g of the target compound H4 in 57% yield.
The target product structure was tested according to mass spectrometry (HRMS):
C 69 H 46 N 4 s, calculated molecular weight: 884.3, test value: 885.1;
theoretical value of elemental analysis: c:85.49, S:3.62, N:6.33, H:4.56;
elemental analysis test value: c:85.13, S:3.42, N:6.81, H:4.60.
example 5
The embodiment provides an electron transport material, which has the following structure:
the preparation method comprises the following steps:
3g of intermediate A7,4g of intermediate A6,0.16mmol of palladium acetate, 0.32mmol of tri-tert-butylphosphine, 9.6mmol of potassium carbonate and 50mL of tetrahydrofuran were mixed under an argon atmosphere, stirred at 125 ℃ for 12H, and the solid obtained from the reaction was purified by silica gel column chromatography and recrystallization to give 3.9g of the target compound H5 in 56% yield.
The target product structure was tested according to mass spectrometry (HRMS):
C 62 H 41 N 5 calculated molecular weight value: 855.35, test values: 856.04;
theoretical value of elemental analysis: c:86.93, N:8.11, H:4.96;
elemental analysis test value: c:86.95, N:8.14, H:4.92.
example 6
The embodiment provides an electron transport material, which has the following structure:
the preparation method comprises the following steps:
3g of intermediate A8,4g of intermediate A6,0.16mmol of palladium acetate, 0.32mmol of tri-tert-butylphosphine, 9.6mmol of potassium carbonate and 50mL of tetrahydrofuran were mixed under an argon atmosphere, stirred at 125 ℃ for 12H, and the solid obtained from the reaction was purified by silica gel column chromatography and recrystallization to give 4.5g of the target compound H6 in 65% yield.
Target product structure was tested according to mass spectrometry (HRMS):
C 62 H 41 N 5 calculated molecular weight value: 855.35, test value: 856.04;
theoretical value of elemental analysis: c:86.92, N:8.13, H:4.94;
elemental analysis test value: c:86.97, N:8.11, H:4.93.
application example 1
An OLED device comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked; the material composition of each layer is as follows:
anode: indium Tin Oxide (ITO) with a thickness of 60 nm;
hole injection layer: the thickness is 60nm and HIL;
hole transport layer: 80nm in thickness, HTL;
light-emitting layer: the thickness is 30nm, and the main material is BH 3 The doping agent is BD, and the mass ratio of the BD to the BD is 95;
electron transport layer: an electron transport material (compound H1) provided in example 1 of the present invention, having a thickness of 40 nm;
electron injection layer: the thickness is 2nm, liF;
cathode: 150nm thick, aluminum.
The hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode of the OLED device are prepared by a vacuum deposition method.
Application example 2
An OLED device differed from application example 1 only in that compound H1 in the electron transport layer was replaced with the electron transport material (compound H2) provided in example 2 of the present invention.
Application example 3
An OLED device which differs from application example 1 only in that the compound H1 in the electron transport layer was replaced with the electron transport material (compound H3) provided in example 3 of the present invention.
Application example 4
An OLED device which differs from application example 1 only in that the compound H1 in the electron transport layer was replaced with the electron transport material (compound H4) provided in example 4 of the present invention.
Application example 5
An OLED device which differs from application example 1 only in that the compound H1 in the electron transport layer was replaced with the electron transport material (compound H5) provided in example 5 of the present invention.
Application example 6
An OLED device differed from application example 1 only in that compound H1 in the electron transport layer was replaced with the electron transport material (compound H6) provided in example 6 of the present invention.
Application comparative example 1
An OLED device, which differs from application example 1 only in that compound H1 in the electron transport layer is replaced with the electron transport material (compound D1) provided in example 1 of the present invention, the structural formula is as follows:
comparative application example 2
An OLED device, which differs from application example 1 only in that compound H1 in the electron transport layer is replaced with the electron transport material (compound D2) provided in example 1 of the present invention, the structural formula is as follows:
the preparation of D2 differs from example 1 in that A1 is replaced by A9
The target product structure was tested according to mass spectrometry (HRMS):
C 45 H 30 N 4 calculated molecular weight value: 626.25, test value: 626.76;
theoretical value of elemental analysis: c:86.24, N:8.94, H:4.82;
elemental analysis test value: c:86.18, N:8.98, H:4.86.
performance testing of the OLED devices:
the OLED devices provided in application examples 1 to 6 and application comparative examples 1 to 2 were subjected to a test of luminous efficiency, and measured for electroluminescence spectrum and current-voltage-luminous density characteristics (IUL characteristics) at 1000cd/m 2 The lifetime TL1 is defined as the time during which the brightness drops from the initial brightness to a certain proportion L1 during operation at constant current, and therefore T95 is the time during which the brightness drops to 95% of its initial value during operation, in the above test 40mA/cm was used 2 As operating conditions.
The performance test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, the electron transport material provided by the invention is suitable for being used as an electron transport layer material in an OLED device, the current efficiency of the OLED device using the electron transport material as the electron transport layer reaches 7.12-8.25 Cd/A, T95 reaches 280-310 h, and the driving voltage is reduced to 3.58-3.64V, so that the luminous efficiency of the device is effectively improved, the service life of the device is prolonged, and the driving voltage is reduced.
In the charge transport material provided by the invention, a specific parent-nucleus structure and a plurality of substituents are mutually cooperated, so that the charge transport material has excellent charge transfer capacity, and the change of the parent-nucleus structure (application comparative example 1) or the deletion of the substituents (application comparative example 2) can cause the reduction of the transport efficiency of the material and influence the performance of a device.
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 (10)
1. An electron transport material having a structure according to formula I:
wherein L is 1 And L 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C3-C60 cycloalkyl group, and a substituted or unsubstituted C2-C60 heterocyclic group;
Ar 1 and Ar 2 At least one selected from the group consisting of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C2-C60 heterocyclic group, and a substituted or unsubstituted C3-C60 cycloalkyl group.
2. The electron transport material of claim 1, wherein the hetero atom in the heterocyclic group is selected from any one of O, N, S, and Si.
3. The electron transport material of claim 1 or 2, wherein the arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, anthracenylene, phenanthrenylene, or fluorenylene;
preferably, the aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl or spirofluorenyl;
preferably, the heteroaryl group is selected from any one of N-phenylcarbazolyl, furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, carbazolyl, acridinyl, imidazolyl, oxazolyl, thiazolyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, benzimidazolyl, quinolyl or isoquinolyl.
4. The electron transport material of any of claims 1-3, wherein L is 1 And L 2 Each independently selected from a single bond or a C6-C12 arylene;
preferably, ar is 1 And Ar 2 Each independently selected from at least one of the following groups:
wherein "-" represents the linkage of the group.
5. The electron transport material of any of claims 1-4, wherein the electron transport material comprises any one of the following compounds H1-H14 or a combination of at least two of the following compounds:
6. a method for preparing an electron transport material according to any of claims 1 to 5, comprising the steps of:
will be provided with
And with
L 1 、L 2 、Ar 1 and Ar 2 Each independently having the same limitations as claim 1;
and X is halogen.
7. The production method according to claim 6, wherein the catalyst is a palladium catalyst;
preferably, said X is Cl.
8. An OLED device comprising at least an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode, which are sequentially stacked, wherein the material of the electron transport layer comprises the electron transport material according to any one of claims 1 to 6.
9. The OLED device of claim 8, wherein the hole injection layer has a thickness of 55-65nm;
preferably, the thickness of the hole transport layer is 75-85nm;
preferably, the thickness of the light emitting layer is 25 to 35nm;
preferably, the thickness of the electron transport layer is 35-45nm;
preferably, the thickness of the electron injection layer is 1 to 3nm.
10. An electronic device, characterized in that it comprises an OLED device according to claim 8 or 9.
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