CN117384083A - Deuterated organic electron donor material, preparation method and OLED device - Google Patents
Deuterated organic electron donor material, preparation method and OLED device Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 25
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 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 claims description 12
- 238000011097 chromatography purification Methods 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 10
- 229940126214 compound 3 Drugs 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 238000005086 pumping Methods 0.000 claims description 9
- 229940125898 compound 5 Drugs 0.000 claims description 7
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- -1 Alkoxyaryl radicals Chemical class 0.000 claims description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005213 alkyl heteroaryl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000004768 bromobenzenes Chemical class 0.000 claims description 3
- 150000001716 carbazoles Chemical class 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000010494 dissociation reaction Methods 0.000 abstract description 4
- 230000005593 dissociations Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 238000001228 spectrum Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 3
- 125000004431 deuterium atom Chemical group 0.000 description 3
- 238000013086 organic photovoltaic Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000005445 isotope effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001975 deuterium Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/002—Heterocyclic compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
The invention provides a deuterated organic electron donor material, a preparation method and an OLED device. The molecular structural formulas of the deuterated organic electron donor materials are respectively shown as the formula (I) and the formula (II):R 1 ，R 2 ，R 3 and R is R 4 Hydrogen or deuterium;R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 and R is R 12 Hydrogen or deuterium. By optimising organic electron donor materialsThe invention effectively improves the device stability of the organic light emitting diode and prolongs the service life of the OLED device. The OLED device EQE is large and the service life is prolonged, which is mainly beneficial to the fact that the deuterated organic electron donor material has high bond dissociation energy and low molecular vibration zero energy.
Description
Technical Field
The invention relates to an organic electron donor material, in particular to a deuterated organic electron donor material, a preparation method and an OLED device.
Background
Organic Light Emitting Diodes (OLEDs) are widely used in electronic products for display and illumination under increasing development. The OLED has the advantages of fast response speed, thin thickness, wide viewing angle, wide use temperature range, flexible display, etc., and is considered as an emerging application technology for flat and foldable displays of the next generation. Driven by the foregoing advantages, intensive research and development has resulted in improved External Quantum Efficiency (EQE) of organic light emitting diode devices, reduced roll-off of efficiency and broader emission of the uv-vis color range. However, device lifetime remains a major obstacle to electronic displays. One of the reasons for limiting the lifetime of the device is exciton annihilation, such as triplet-triplet and triplet-polaron interactions. These effects are typically caused by high energy triplet excitons generated under electrical stress and radiation, and instability of the excited molecules can lead to molecular degradation and formation of products thereof, thereby quenching the efficiency and lifetime of the OLED device. It is therefore important to design molecules with high bond dissociation energies to withstand unwanted electrochemical degradation reactions.
The stability of the photoelectric material in the OLED device is regulated by influencing the bonding reaction mechanism, molecular dynamics and other properties based on the Kinetic Isotope Effect (KIE). The substitution of hydrogen/deuterium atoms in the molecule is an example of one of KIE, and research indicates that the chemical bond vibration frequency of the organic compound after deuterium substitution is obviously reduced, the strength of the chemical bond is enhanced, and chemical reactions such as electrophilic substitution reaction, oxidation reaction, proton abstraction reaction and the like are greatly slowed down. Therefore, there is a need to develop deuterated photovoltaic materials with chemical stability to increase the lifetime of OLED devices.
US9233922B2 discloses an organic electron donor material (mCP) which is widely applied to the light emitting layers of OLED devices of different color gamuts due to the relationship of high triplet energy levels, and is responsible for absorbing exciton energy and transferring to the light emitting material for effective light emission of the device. However, the stability of the organic photovoltaic device is poor due to the fact that the molecular bonds of the organic electron donor material are easily distorted and rotated.
Small Sci.2021, 2000057 discloses a deuterated organic electron donor material (PYD 2Cz-d 16 ) Since 19 hydrogen atoms are replaced by 16 deuterium atoms, this results in a material with a denser molecular arrangement and more balanced charge transport characteristics across the device. The OLED device is 1000cd m 2 At the initial luminance of (1), the device half-life (LT 50 ) The improvement is doubled from 17 hours to 40 hours.
Acs Appl, mate. Interfaces,2023, 15, 7255-7262 demonstrated the relationship between deuteration degree and device lifetime. LT by increasing the number of deuterium atoms of an organic electron donor material (PNA) from 5 to 22 90 The device lifetime is extended four times from 8.2 hours to 33.6 hours. Because the heavier isotopes cause a slower kinetic rate, they slow down undesirable molecular adducts formed by chemical reactions at high temperature and current density pressures, thereby increasing device lifetime.
However, none of the above organic electron donor materials have completely replaced a hydrogen atom with a deuterium atom, and the maximum kinetic isotope effect is not achieved.
How to improve the device stability of an organic light emitting diode and the service life of an OLED device by optimizing an organic electron donor material is a challenge in the prior art.
It should be noted that the information disclosed in the above background section is only for understanding the background of the present application and thus may include information that does not form the prior art that is already known to those of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a deuterated organic electron donor material, a preparation method and an OLED device.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a deuterated organic electron donor material has a molecular structural formula in which at least one hydrogen is replaced by deuterium, and is shown in formula (I) and formula (II)
[ type (I)]
R 1 ，R 2 ，R 3 And R is R 4 Hydrogen or deuterium;
[ type (II)]
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 And R is R 12 Hydrogen or deuterium.
Further:
for formula (I), X 1 And X is 2 Carbazole having different deuterium amounts.
For formula (I), X 1 And X is 2 The method comprises the following steps:
for formula (II), X 1 ，X 2 And X is 3 Carbazole having different deuterium amounts.
For formula (II), X 1 ，X 2 And X is 3 The method comprises the following steps:
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，X 1 ，X 2 and X is 3 Is deuterium, C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 1 -C 30 Alkylaryl, C 1 -C 30 Alkyl heteroaryl, C 1 -C 30 Alkoxyaryl radicals C 1 -C 30 Silicon-based aryl or C1-C 30 Alkoxy heteroaryl.
A method for preparing a deuterated organic electron donor material, comprising the following process for preparing any one of the compounds:
dripping deuterated benzene into mixed water solution of concentrated sulfuric acid and nitric acid under ice bath, and performing extraction, drying, filtration, concentration and pumping drying after reaction to obtain a compound 1;
mixing the compound 1, ferric trichloride and N-bromosuccinimide, and performing extraction, drying, filtration, concentration and suction, chromatographic purification and vacuum drying after the reaction to obtain a compound 2;
dissolving the compound 2 in acetic acid, adding iron powder for a plurality of times, adding sodium bicarbonate for neutralization after reaction, and then carrying out extraction, drying, filtration, concentration and drainage, chromatographic purification and vacuum drying to obtain a compound 3;
under the protection of nitrogen, dissolving the compound 3 in hydrobromic acid under ice bath, adding sodium nitrate, adding cuprous bromide, extracting, drying, filtering, concentrating, pumping, purifying by chromatography, and vacuum drying to obtain a compound 4;
under the protection of nitrogen, dissolving a compound 4, deuterated carbazole, sodium tert-butoxide, tri-tert-butylphosphine and tris (dibenzylideneandene acetone) dipalladium (0) in toluene, and performing extraction, drying, filtration, concentration and drying, chromatography purification and vacuum drying after reaction to obtain a compound 5;
under the protection of nitrogen, dissolving deuterated bromobenzene, deuterated aniline, sodium tert-butoxide, tri-tert-butylphosphine and tris (dibenzylideneandene acetone) dipalladium (0) in toluene, and then extracting, drying, filtering, concentrating, drying, purifying by chromatography and drying in vacuum to obtain a compound 6;
under the protection of nitrogen, dissolving compound 6, potassium iodate and potassium iodide in N, N-dimethylformamide, and then carrying out extraction, drying, filtration, concentration and pumping, chromatographic purification and vacuum drying after the reaction to obtain compound 7;
under the protection of nitrogen, dissolving the compound 7, trans-1, 2-cyclohexanediamine, potassium phosphate and copper iodide in 1, 4-dioxane, and then carrying out extraction, drying, filtration, concentration and pumping, chromatographic purification and vacuum drying after the reaction to obtain the compound 8.
An OLED device employs the deuterated organic electron donor material.
The invention has the following beneficial effects:
the invention provides a deuterated organic electron donor material, a preparation method and an OLED device. By optimizing the organic electron donor material, the invention effectively improves the device stability of the organic light emitting diode and prolongs the service life of the OLED device.
The compound of the embodiment of the invention is made into a device, and the device life is prolonged while the EQE of the device is large. This is mainly benefited by the fact that the deuterated organic electron donor material provided by the invention has higher bond dissociation energy and lower molecular vibration zero energy. The material designed by the invention is applied to the OLED evaporation process, and the service life of the device is obviously prolonged.
Other advantages of embodiments of the present invention are further described below.
Drawings
FIG. 1 is a hydrogen spectrum of compound 1 of the present invention.
FIG. 2 is a carbon spectrum of compound 1 of the present invention.
FIG. 3 is a mass spectrum of compound 1 of the present invention.
FIG. 4 is a hydrogen spectrum of compound 2 of the present invention.
FIG. 5 is a carbon spectrum of compound 2 of the present invention.
FIG. 6 is a mass spectrum of compound 2 of the example of the present invention.
FIG. 7 is a hydrogen spectrum of compound 3 of the present invention.
FIG. 8 is a carbon spectrum of compound 3 of the present invention.
FIG. 9 is a mass spectrum of compound 3 of the present invention.
FIG. 10 is a hydrogen spectrum of compound 4 of the present invention.
FIG. 11 is a carbon spectrum of compound 4 of the present invention.
FIG. 12 is a mass spectrum of compound 4 of the present invention.
FIG. 13 is a hydrogen spectrum of compound 5 of the present invention.
FIG. 14 is a carbon spectrum of compound 5 of the present invention.
FIG. 15 is a mass spectrum of compound 5 of the present invention.
FIG. 16 is a hydrogen spectrum of compound 6 of the example of the present invention.
FIG. 17 is a carbon spectrum of compound 6 of the present invention.
FIG. 18 is a mass spectrum of compound 6 of the present invention.
FIG. 19 is a hydrogen spectrum of compound 7 of the present invention.
FIG. 20 is a carbon spectrum of compound 7 of the present invention.
FIG. 21 is a mass spectrum of compound 7 of the present invention.
FIG. 22 is a hydrogen spectrum of compound 8 of the present invention.
FIG. 23 is a carbon spectrum of compound 8 of the present invention.
FIG. 24 is a mass spectrum of compound 8 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its applications.
The embodiment of the invention provides a deuterated organic electron donor material, which comprises deuterated d-mCP and d-TCTA and a synthesis process thereof. The molecular structural formulas of the deuterated d-mCP and d-TCTA are at least one hydrogen replaced by deuterium, and the molecular structural formulas are respectively shown in the formula (I) and the formula (II):
[ type (I)]
R 1 ，R 2 ，R 3 And R is R 4 Is hydrogen or deuterium, preferably R 1 ，R 2 ，R 3 And R is R 4 Deuterium.
X 1 And X is 2 Carbazole having different deuterium amounts. Preferably X 1 ，X 2 Is that
[ type (II)]
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 And R is R 12 Hydrogen or deuterium. Preferably, R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 And R is R 12 Deuterium.
X 1 ，X 2 And X is 3 Carbazole having different deuterium amounts. Preferably X 1 ，X 2 And X is 3 Is that
In some embodiments, a range of new materials are derived according to the synthetic formulas (I), (II) and synthetic routes of the present invention.
Wherein R is 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，X 1 ，X 2 And X is 3 Deuterium is,C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 1 -C 30 Alkylaryl, C 1 -C 30 Alkyl heteroaryl, C 1 -C 30 Alkoxyaryl radicals C 1 -C 30 Silicon-based aryl or C1-C 30 Alkoxy heteroaryl. The above groups each bear a different number of deuterium atoms, as shown below;
[ method for producing electron donor Material Compound ]
The preparation methods of the electron donor material compound of the present invention are two, and are respectively described below.
The preparation method of the first electron donor material compound comprises the following steps:
[ reaction type (I) ]
Preparation of Compound 1 (d-mCP):
deuterated benzene (5.0 g,59.5 mmol) was slowly added dropwise to a mixed aqueous solution of concentrated sulfuric acid (11.7 g,119.0 mmol) and nitric acid (5.6 g,89.2 mmol) under an ice bath, and the mixture was stirred at room temperature for 1 hour. After the reaction is finished, petroleum ether is added for extraction, and the organic layer is dried by anhydrous magnesium sulfate, filtered and concentrated and pumped by a rotary concentrator. After drying in vacuo, compound 1 (4.4 g, yield: 88%) was obtained as a yellow liquid. 13 C NMR (101 MHz, deuterated chloroform) delta 148.11,134.35,134.10,133.85,129.08,128.83,128.58,123.39,123.13,122.8. High resolution ESI-MS analysis results C 6 D 5 NO 2 128.0634; the detection value was 128.1070 ([ M)] + ).
Preparation of Compound 2 (d-mCP):
compound 1 (4.4 g,34.3 mmol), ferric trichloride (5.6 g,34.3 mmol) and N-bromosuccinimide (6.1 g,34.3 mmol) were first mixed, heated to 150℃and stirred for 2 hours. After the reaction is finished, ethyl acetate is added for extraction, the organic layer is dried by anhydrous magnesium sulfate, filtered, and concentrated and pumped by a rotary concentrator. Then, purification was further performed by silica gel column chromatography, and the obtained product was dried under vacuum to obtain compound 2 (3.7 g, yield: 84%) as a white solid. 13 C NMR (126 MHz, deuterated chloroform) delta 148.71,137.42,137.22,137.01,130.31,130.11,129.90,126.74,126.52,126.31,122.66,122.02,121.82,121.61. High resolution ESI-MS analysis results C 6 D 4 BrNO 2 Theoretical value 204.9676; the detection value was 205.9877 ([ M+1)] + )
Preparation of Compound 3 (d-mCP):
compound 2 (3.7 g,18.0 mmol) was dissolved in acetic acid (25 ml), and iron powder (10.0 g,179.6 mmol) was added in portions and heated to 50℃and stirred for 6 hours. After the reaction is finished, adding sodium bicarbonate for neutralization, adding ethyl acetate for extraction, drying an organic layer by anhydrous magnesium sulfate, filtering, and concentrating and pumping by a rotary concentrator. Then, purification was further performed by silica gel column chromatography, and after vacuum drying, compound 3 (2.9 g, yield: 78.4%) was obtained as a dark gray solid. 13 C NMR (101 MHz, deuterated chloroform) delta 147.68,130.36,130.12,129.87,122.84,122.82,121.27,121.00,120.75,117.84,117.79,117.55,117.30,113.55,113.29,113.05,31.53,29.73. High resolution ESI-MS analysis results C 30 H 2 D 4 BrN 174.9935; the detection value was 174.9943 ([ M)] + ).
Preparation of Compound 4 (d-mCP):
compound 3 (2.9 g,16.5 mmol) was dissolved in hydrobromic acid (20 ml) under nitrogen and then sodium nitrate (10.0 g,179.6 mmol) was added under an ice bath. After 30 minutes, cuprous bromide (3.5 g 24.7 mmol) was added, heated to 60℃and stirred for 2 hours. After the reaction is finished, adding dichloroMethane is extracted, the organic layer is dried over anhydrous magnesium sulfate, filtered, and concentrated and drained by a rotary concentrator. Then, purification was further performed by silica gel column chromatography, and vacuum drying was performed to obtain a transparent liquid compound 4 (1.4 g, yield: 48.3%). 1 H NMR (400 MHz, deuterated chloroform) delta 7.67 (s, 1H), 7.42 (s, 1H). 13 C NMR (101 MHz, deuterated chloroform) delta 134.15,133.84,133.58,130.83,130.58,130.33,130.10,129.81,129.55,122.89,122.78,29.70.ESI-MS analysis results C 6 D 4 Br 2 237.8931; the detection value was 237.8697 ([ M)] + ).
Preparation of Compound 5 (d-mCP):
compound 4 (1.4 g,5.8 mmol), deuterated carbazole (2.0 g,11.7 mmol), sodium t-butoxide (1.3 g,13.4 mmol), tri-t-butylphosphine (2.4 g,11.7 mmol) and tris (dibenzylideneandene acetone) dipalladium (0) (0.5 g,0.1 mmol) were dissolved in toluene (15 ml), heated to 110℃and stirred for 6 hours under nitrogen. After the reaction is finished, dichloromethane is added for extraction, the organic layer is dried by anhydrous magnesium sulfate, filtered, and concentrated and pumped by a rotary concentrator. Then, purification was further performed by silica gel column chromatography, and then, vacuum drying was performed to obtain compound 5 (0.9 g, yield: 64.3%) as a white solid. 1 H NMR (400 MHz, deuterated chloroform) δ8.13 (s, 1H), 7.81 (s, 1H), 7.67 (s, 1H), 7.53 (s, 1H), 7.42 (s, 1H), 7.29 (s, 1H). 13 C NMR (101 MHz, deuterated chloroform) delta 140.60,139.41,139.34,126.10,126.00,125.72,125.65,125.48,125.36,125.19,125.13,124.90,124.65,123.66,123.58,120.42,120.27,120.16,119.90,119.65,109.63,109.38,109.14. High resolution ESI-MS analysis results C 30 D 20 N 2 428.2882; the detection value was 428.2875 ([ M)] + ).
The preparation method of the second electron donor material compound comprises the following steps:
[ reaction type (II) ]
Preparation of Compound 6 (d-TCTA):
under nitrogen environmentUnder this condition, deuterated bromobenzene (1.4 g,5.8 mmol), deuterated aniline (2.0 g,11.7 mmol), sodium tert-butoxide (1.3 g,13.4 mmol), tri-tert-butylphosphine (2.4 g,11.7 mmol) and tris (dibenzylideneandene acetone) dipalladium (0) (0.5 g,0.1 mmol) were dissolved in toluene (15 ml), heated at 110℃and stirred for 6 hours. After the reaction is finished, dichloromethane is added for extraction, the organic layer is dried by anhydrous magnesium sulfate, filtered, and concentrated and pumped by a rotary concentrator. Then, purification was further performed by silica gel column chromatography, and then, vacuum drying was performed to obtain compound 6 (0.9 g, yield: 64.3%) as a white solid. 1 H NMR (400 MHz, deuterated chloroform) delta 7.08 (s, 3H), 6.98 (s, 2H). 13 C NMR (101 MHz, deuterated chloroform) delta 147.71,128.92,128.67,128.44,123.92,123.68,123.43,122.36,122.12,121.87. High resolution ESI-MS analysis results C 18 D 15 N260.2146; the detection value was 260.2155 ([ M)] + ).
Preparation of Compound 7 (d-TCTA):
compound 6 (1.4 g,5.8 mmol), potassium iodate (2.0 g,11.7 mmol) and potassium iodide (1.3 g,13.4 mmol) were dissolved in N, N-dimethylformamide (15 ml), heated to 120℃and stirred for 12 hours under nitrogen. After the reaction is finished, ethyl acetate is added for extraction, the organic layer is dried by anhydrous magnesium sulfate, filtered, and concentrated and pumped by a rotary concentrator. Then, purification was further performed by silica gel column chromatography, and compound 7 (0.9 g, yield: 64.3%) was obtained as a white solid after drying in vacuo. 1 H NMR (400 MHz, deuterated chloroform) delta 7.53 (s, 1H), 7.35 (s, 1H), 6.93 (s, 3H), 6.81 (s, 4H). 13 C NMR (126 MHz, deuterated chloroform) delta 146.64,146.54,146.44,145.82,138.34,138.21,138.01,137.80,132.34,132.13,131.93,125.88,125.75,125.59,116.03,115.92,115.81,86.22,86.09,85.96. High resolution ESI-MS analysis results C 18 D 12 I 3 N634.8857; the detection value was 634.8855 ([ M)] + ).
Preparation of Compound 8 (d-TCTA):
under nitrogen atmosphere, compound 6 (1.4 g,5.8 mmol), trans-1, 2-cyclohexanediamine (2.0 g,11.7 mmol), potassium phosphate (1.4 g,5.8 mmol) and copper iodide (1.3 g,13.4 mmol) were dissolved in 1, 4-dioxane (15 ml), heated at 150℃and stirred for 12 hours. After the reaction is finished, adding ethyl acetate intoThe organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated by a rotary concentrator. Then, purification was further performed by silica gel column chromatography, and then, vacuum drying was performed to obtain compound 8 (0.9 g, yield: 64.3%) as a white solid. 1 H NMR (400 MHz, deuterated chloroform) delta 8.10 (s, 2H), 7.45 (s, 2H), 7.38 (s, 1H), 7.24 (s, 1H). 13 C NMR (126 MHz, deuterated chloroform) delta 146.24,140.99,140.91,132.73,125.72,125.44,125.22,124.91,123.35,123.27,123.22,120.27,119.83,119.72,109.68. High resolution ESI-MS analysis results C 54 D 36 N 4 776.52; the detection value was 776.5175 ([ M)] + ).
The compounds of the examples of the present invention were fabricated into devices and the current densities, luminance and photoluminescence spectra of the photovoltaic devices were measured at different voltages using Keithley 2400 and then divided by the current to give the current of the organic photovoltaic devices at different voltages. The organic photovoltaic devices fabricated according to the examples were tested for brightness and radiant fluence at different voltages using the PR-OLEDLT-16 test lifetime degradation test. The external quantum efficiency EQE and the service life of the device are obtained according to the current density and the brightness of the organic photoelectric device under different voltages. The deuterated organic electron donor material provided by the invention has higher bond dissociation energy and lower molecular vibration zero energy, and the service life of the prepared device is obviously prolonged when the material is applied to an OLED evaporation process.
The background section of the present invention may contain background information about the problems or environments of the present invention and is not necessarily descriptive of the prior art. Accordingly, inclusion in the background section is not an admission of prior art by the applicant.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention. In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "preferred embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Those skilled in the art may combine and combine the features of the different embodiments or examples described in this specification and of the different embodiments or examples without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. A deuterated organic electron donor material is characterized in that at least one hydrogen in the molecular structural formula is replaced by deuterium, and the deuterium is respectively shown as a formula (I) and a formula (II)
[ type (I)]
R 1 ，R 2 ，R 3 And R is R 4 Hydrogen or deuterium;
[ type (II)]
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 And R is R 12 Hydrogen or deuterium.
2. The deuterated organic electron donor material according to claim 1, wherein for formula (I)，X 1 And X is 2 Carbazole having different deuterium amounts.
3. The deuterated organic electron donor material according to claim 2 wherein, for formula (I), X is 1 And X is 2 The method comprises the following steps:
4. the deuterated organic electron donor material according to claim 1 wherein, for formula (II), X is 1 ，X 2 And X is 3 Carbazole having different deuterium amounts.
5. The deuterated organic electron donor material according to claim 4 wherein, for formula (II), X is 1 ，X 2 And X is 3 The method comprises the following steps:
6. the deuterated organic electron donor material according to claim 1 wherein R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 ，R 9 ，R 10 ，R 11 ，R 12 ，X 1 ，X 2 And X is 3 Is deuterium, C 1 -C 30 Alkyl, C 1 -C 30 Alkoxy, C 1 -C 30 Alkylaryl, C 1 -C 30 Alkyl heteroaryl, C 1 -C 30 Alkoxyaryl radicals C 1 -C 30 Silicon-based aryl or C1-C 30 Alkoxy heteroaryl.
7. A method for preparing a deuterated organic electron donor material, comprising the following steps of:
dripping deuterated benzene into mixed water solution of concentrated sulfuric acid and nitric acid under ice bath, and performing extraction, drying, filtration, concentration and pumping drying after reaction to obtain a compound 1;
mixing the compound 1, ferric trichloride and N-bromosuccinimide, and performing extraction, drying, filtration, concentration and suction, chromatographic purification and vacuum drying after the reaction to obtain a compound 2;
dissolving the compound 2 in acetic acid, adding iron powder for a plurality of times, adding sodium bicarbonate for neutralization after reaction, and then carrying out extraction, drying, filtration, concentration and drainage, chromatographic purification and vacuum drying to obtain a compound 3;
under the protection of nitrogen, dissolving the compound 3 in hydrobromic acid under ice bath, adding sodium nitrate, adding cuprous bromide, extracting, drying, filtering, concentrating, pumping, purifying by chromatography, and vacuum drying to obtain a compound 4;
under the protection of nitrogen, dissolving a compound 4, deuterated carbazole, sodium tert-butoxide, tri-tert-butylphosphine and tris (dibenzylideneandene acetone) dipalladium (0) in toluene, and performing extraction, drying, filtration, concentration and drying, chromatography purification and vacuum drying after reaction to obtain a compound 5;
under the protection of nitrogen, dissolving deuterated bromobenzene, deuterated aniline, sodium tert-butoxide, tri-tert-butylphosphine and tris (dibenzylideneandene acetone) dipalladium (0) in toluene, and then extracting, drying, filtering, concentrating, drying, purifying by chromatography and drying in vacuum to obtain a compound 6;
under the protection of nitrogen, dissolving compound 6, potassium iodate and potassium iodide in N, N-dimethylformamide, and then carrying out extraction, drying, filtration, concentration and pumping, chromatographic purification and vacuum drying after the reaction to obtain compound 7;
under the protection of nitrogen, dissolving the compound 7, trans-1, 2-cyclohexanediamine, potassium phosphate and copper iodide in 1, 4-dioxane, and then carrying out extraction, drying, filtration, concentration and pumping, chromatographic purification and vacuum drying after the reaction to obtain the compound 8.
8. An OLED device employing a deuterated organic electron donor material as defined in any one of claims 1-6.
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