CN113072571A - Seven-membered ring thermal activation delayed fluorescent material, preparation method thereof and organic light-emitting device - Google Patents
Seven-membered ring thermal activation delayed fluorescent material, preparation method thereof and organic light-emitting device Download PDFInfo
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- CN113072571A CN113072571A CN202110238720.1A CN202110238720A CN113072571A CN 113072571 A CN113072571 A CN 113072571A CN 202110238720 A CN202110238720 A CN 202110238720A CN 113072571 A CN113072571 A CN 113072571A
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- membered ring
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- 239000000463 material Substances 0.000 title claims abstract description 86
- 230000003111 delayed effect Effects 0.000 title claims abstract description 57
- 238000007725 thermal activation Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 11
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical group C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 8
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical group C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 8
- 229930192474 thiophene Natural products 0.000 claims abstract description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical group 0.000 claims abstract description 4
- 239000013067 intermediate product Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 150000004982 aromatic amines Chemical class 0.000 claims description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- RKWWASUTWAFKHA-UHFFFAOYSA-N 1-bromo-2,3-difluorobenzene Chemical compound FC1=CC=CC(Br)=C1F RKWWASUTWAFKHA-UHFFFAOYSA-N 0.000 claims description 3
- SWELJVAWQMCJLG-UHFFFAOYSA-N 5-bromo-2-chloro-1,3-difluorobenzene Chemical compound FC1=CC(Br)=CC(F)=C1Cl SWELJVAWQMCJLG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 8
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000009825 accumulation Methods 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- UMHSKYSHOIGDPE-UHFFFAOYSA-N pyridine;quinoline Chemical group C1=CC=NC=C1.N1=CC=CC2=CC=CC=C21 UMHSKYSHOIGDPE-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- KCBAMQOKOLXLOX-BSZYMOERSA-N CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O Chemical compound CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O KCBAMQOKOLXLOX-BSZYMOERSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229940125833 compound 23 Drugs 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- ZBELDPMWYXDLNY-UHFFFAOYSA-N methyl 9-(4-bromo-2-fluoroanilino)-[1,3]thiazolo[5,4-f]quinazoline-2-carboximidate Chemical compound C12=C3SC(C(=N)OC)=NC3=CC=C2N=CN=C1NC1=CC=C(Br)C=C1F ZBELDPMWYXDLNY-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical group C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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Abstract
The invention discloses a seven-membered ring thermal activation delayed fluorescence material, a preparation method thereof and an organic light-emitting device, wherein the seven-membered ring thermal activation delayed fluorescence material has a chemical structure general formula as follows:
wherein Ar is1‑Ar4Each independently selected from benzene, thiophene, furan, pyridine or substituted aryl or heteroaryl as described above, R1‑R12Each independently selected from one of hydrogen, deuterium, cyano or alkyl chain, X is selected from hydrogen, deuterium, halogen, cyano, alkyl chain or benzene, thiophene, furan, carbazole, pyridineQuinoline, isoquinoline and substituted aryl or heteroaryl groups as described above. The seven-membered ring is introduced, so that the accumulation of materials can be effectively improved, intermolecular triplet state quenching is reduced, the efficiency roll-off is reduced, the stability of a device is improved, and the service life of the device is prolonged; meanwhile, a unique boron-nitrogen multiple resonance structure is adopted to endow the material with a narrower fluorescence emission spectrum and a higher external quantum efficiency value.
Description
Technical Field
The invention relates to the technical field of organic display, in particular to a seven-membered ring thermal activation delayed fluorescent material, a preparation method thereof and an organic light-emitting device.
Background
Organic Light Emitting Diodes (OLEDs) are a new generation of optical display technology, have the advantages of low driving voltage, low power consumption, high brightness, high efficiency, high contrast, lightness, thinness, no viewing angle dependence, high reaction speed and the like, and have very wide application prospects in the aspects of flat panel display, high-efficiency illumination, flexible wearable equipment and the like.
The light emitting material is the core material of the OLED, and three generations of light emitting materials, i.e. fluorescent material, phosphorescent material and Thermally Activated Delayed Fluorescence (TADF) material, are currently developed. Among them, the fluorescent material has low efficiency, the phosphorescent material needs to use noble metal and the blue phosphorescent material has poor stability, and the TADF material has internal quantum efficiency of 100% and low cost, so it is the research hotspot with the most commercial prospect at present.
The currently widely used TADF material has a large value of Full Width at Half Maximum (FWHM) of a fluorescence emission spectrum, which results in low color purity and poor monochromaticity of the device. The teaching of 2016 of the university of Guangxi, Japan, T.Hatekeyama proposed a unique boron-nitrogen multiple resonance structure (patent publication No.: WO2020039930A1) that somewhat narrowed the fluorescence emission spectrum of TADF, but the severe roll-off in efficiency affected the light stability and operating life of the device.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a seven-membered ring thermal activation delayed fluorescence material, a preparation method thereof and an organic light-emitting device, and aims to solve the problems of poor device light stability and short working life caused by serious efficiency roll-off of the conventional thermal activation delayed fluorescence material.
The technical scheme of the invention is as follows:
a seven-membered ring thermally activated delayed fluorescence material, wherein the chemical structure general formula is as follows:
wherein Ar is1-Ar4Each independently selected from benzene, thiophene, furan, pyridine or substituted aryl or heteroaryl as described above, R1-R12Each independently selected from one of hydrogen, deuterium, cyano or alkyl chain, X is selected from hydrogen, deuterium, halogen, cyano, alkyl chain or benzene, thiophene, furan, carbazole, pyridine, quinoline, isoquinoline and substituted aryl or heteroaryl as described above.
A preparation method of a seven-membered ring thermal activation delayed fluorescence material comprises the following steps:
dissolving raw material aromatic boric acid and halogenated aromatic groups in a first solvent to obtain a first intermediate product under a first preset reaction condition;
dissolving the first intermediate product in a first solvent, adding sufficient iron powder and a 3% ammonium chloride solution, heating and refluxing, pouring the solution into water, filtering to obtain a filtrate, performing rotary evaporation and concentration, and performing silica gel column separation to obtain a second intermediate product;
dissolving the second intermediate product in a second solvent to obtain a third intermediate product aromatic amine under a second preset reaction condition;
dissolving the third intermediate product and difluorobromobenzene in a third solvent, adding cesium carbonate, heating and refluxing for 24 hours, pouring the solution into water, filtering to obtain a white precipitate, and recrystallizing by using a fourth solvent to obtain a fourth intermediate product;
and after the fourth intermediate product reacts with N-butyllithium at a low temperature, adding boron tribromide to continuously react, adding N, N-diisopropylethylamine, and stirring to react to obtain the seven-membered ring thermal activation delayed fluorescence material.
A preparation method of a seven-membered ring thermal activation delayed fluorescence material comprises the following steps:
dissolving raw material aromatic boric acid and halogenated aromatic groups in a first solvent to obtain a first intermediate product under a first preset reaction condition;
dissolving the first intermediate product in a first solvent, adding sufficient iron powder and a 3% ammonium chloride solution, heating and refluxing, pouring the solution into water, filtering to obtain a filtrate, performing rotary evaporation and concentration, and performing silica gel column separation to obtain a second intermediate product;
dissolving the second intermediate product in a second solvent to obtain a third intermediate product aromatic amine under a second preset reaction condition;
dissolving the third intermediate product aromatic amine and 5-bromo-2-chloro-1, 3-difluorobenzene in a third solvent, adding cesium carbonate, heating and refluxing for 24 hours, pouring the solution into water, filtering to obtain a white precipitate, and recrystallizing by using a fourth solvent to obtain a fifth intermediate product;
a sixth intermediate product of a substituted or unsubstituted aryl or heteroaryl and a fifth intermediate product dissolved in a first solvent under first predetermined reaction conditions;
and after the sixth intermediate product reacts with N-butyllithium at a low temperature, adding boron tribromide to continuously react, adding N, N-diisopropylethylamine, and stirring to react to obtain the seven-membered ring thermal activation delayed fluorescence material.
The preparation method of the seven-membered ring thermal activation delayed fluorescence material comprises the following steps of taking toluene as a first solvent, taking dimethyl sulfoxide as a second solvent, taking N, N-dimethylformamide as a third solvent, and taking ethanol as a fourth solvent.
The preparation method of the seven-membered ring thermal activation delayed fluorescence material comprises the following steps of: the catalyst is 2mol percent of tetratriphenylphosphine palladium and 5 times of potassium carbonate equivalent; the reaction temperature is 100-110 ℃ and the reaction time is 24 hours.
The preparation method of the seven-membered ring thermal activation delayed fluorescence material comprises the following steps of: the catalyst is 2 times of equivalent of potassium tert-butoxide, the reaction temperature is 160 ℃, and the reaction time is 12 hours.
An organic light-emitting device comprises a metal cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer and an indium tin oxide anode in sequence from top to bottom, wherein the light-emitting layer is made of a seven-membered ring thermal activation delay fluorescent material.
Has the advantages that: compared with the prior art, the accumulation of the thermal activation delayed fluorescence material can be effectively improved through the introduction of the seven-membered ring, the intermolecular triplet state quenching is reduced, and the efficiency roll-off is reduced, so that the stability and the service life of a device using the seven-membered ring thermal activation delayed fluorescence material as a light emitting layer are improved; the invention simultaneously adopts a unique boron-nitrogen multiple resonance structure to endow the material with narrower fluorescence emission spectrum and higher external quantum efficiency value. Therefore, the seven-membered ring thermal activation delayed fluorescence material has the advantages of high luminous efficiency, high color purity, small efficiency roll-off and the like when being used as the luminous material of the organic electroluminescent device.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device in embodiment 4 of the present invention.
FIG. 2 is a graph showing the results of the thermal stability test of the seven-membered ring thermally activated delayed fluorescence material in example 1 of the present invention.
FIG. 3 is a graph showing the results of an emission spectrum test of the seven-membered ring thermally activated delayed fluorescence material in example 1 of the present invention.
Detailed Description
The invention provides a seven-membered ring thermal activation delayed fluorescence material, a preparation method thereof and an organic light-emitting device, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Although the prior art proposes that a unique boron-nitrogen multiple resonance structure is adopted to narrow the fluorescence emission spectrum of the thermally activated delayed fluorescence material, the severe efficiency roll-off affects the light stability and the service life of the device.
Based on the above, the invention provides a seven-membered ring thermal activation delayed fluorescence material, which has a chemical structural general formula
Wherein Ar is1-Ar4Each independently selected from benzene, thiophene, furan, pyridine or substituted aryl or heteroaryl as described above, R1-R12Each independently selected from one of hydrogen, deuterium, cyano or alkyl chain, X is selected from hydrogen, deuterium, halogen, cyano, alkyl chain or benzene, thiophene, furan, carbazole, pyridine, quinoline, isoquinoline and substituted aryl or heteroaryl as described above.
The embodiment can effectively improve the accumulation of materials by introducing the seven-membered ring, reduce intermolecular triplet state quenching and reduce efficiency roll-off, thereby improving the stability of the device and prolonging the service life of the device; meanwhile, the unique boron-nitrogen multiple resonance structure is adopted in the embodiment, so that the material has a narrower fluorescence emission spectrum and a higher external quantum efficiency value. Therefore, the seven-membered ring thermal activation delayed fluorescence material has the advantages of high luminous efficiency, high color purity, small efficiency roll-off and the like when being used as the luminous material of the organic electroluminescent device.
In some embodiments, the X is one of the following groups:
In some specific embodiments, the seven-membered ring thermally activated delayed fluorescence material is one of the following 171 chemical structural formulas:
in some embodiments, the present invention further provides a method for preparing the seven-membered ring thermal activation delayed fluorescence material, wherein the chemical reaction process is as follows:
specifically, the preparation method comprises the following steps:
dissolving raw material aromatic boric acid and halogenated aromatic groups in a first solvent to obtain a first intermediate product under a first preset reaction condition;
dissolving the first intermediate product in a first solvent, adding sufficient iron powder and a 3% ammonium chloride solution, heating and refluxing, pouring the solution into water, filtering to obtain a filtrate, performing rotary evaporation and concentration, and performing silica gel column separation to obtain a second intermediate product;
dissolving the second intermediate product in a second solvent to obtain a third intermediate product aromatic amine under a second preset reaction condition;
dissolving the third intermediate product and difluorobromobenzene in a third solvent, adding cesium carbonate, heating and refluxing for 24 hours, pouring the solution into water, filtering to obtain a white precipitate, and recrystallizing by using a fourth solvent to obtain a fourth intermediate product;
and after the fourth intermediate product reacts with N-butyllithium at a low temperature, adding boron tribromide to continuously react, adding N, N-diisopropylethylamine, and stirring to react to obtain the seven-membered ring thermal activation delayed fluorescence material.
In this embodiment, the first solvent is toluene, the second solvent is dimethyl sulfoxide, the third solvent is N, N-dimethylformamide, and the fourth solvent is ethanol. The first preset reaction condition is as follows: the catalyst is 2mol percent of tetratriphenylphosphine palladium and 5 times of potassium carbonate equivalent; the reaction temperature is 100-110 ℃, and the reaction time is 24 hours. The second preset reaction condition is as follows: the catalyst is 2 times of equivalent of potassium tert-butoxide, the reaction temperature is 160 ℃, and the reaction time is 12 hours.
In this embodiment, the aromatic boronic acid is
The halogenated aromatic group is one of the following chemical structural formulas:
in some embodiments, there is also provided another method for preparing a seven-membered ring thermally activated delayed fluorescence material, wherein the chemical reaction process is as follows:
specifically, the preparation method comprises the following steps: :
dissolving the third intermediate product aromatic amine and 5-bromo-2-chloro-1, 3-difluorobenzene in a third solvent, adding cesium carbonate, heating and refluxing for 24 hours, pouring the solution into water, filtering to obtain a white precipitate, and recrystallizing by using a fourth solvent to obtain a fifth intermediate product;
a sixth intermediate product of a substituted or unsubstituted aryl or heteroaryl and a fifth intermediate product dissolved in a first solvent under first predetermined reaction conditions;
and after the sixth intermediate product reacts with N-butyllithium at a low temperature, adding boron tribromide to continuously react, adding N, N-diisopropylethylamine, and stirring to react to obtain the seven-membered ring thermal activation delayed fluorescence material.
In this embodiment, the first solvent is toluene, the second solvent is dimethyl sulfoxide, the third solvent is N, N-dimethylformamide, and the fourth solvent is ethanol. The first preset reaction condition is as follows: the catalyst is 2mol percent of tetratriphenylphosphine palladium and 5 times of potassium carbonate equivalent; the reaction temperature is 100-110 ℃, and the reaction time is 24 hours.
In some embodiments, the present invention further provides an organic light emitting device comprising a light emitting layer, wherein the light emitting layer is made of the seven-membered ring thermally activated delayed fluorescence material according to the present invention.
In some specific embodiments, the organic light emitting device comprises, from top to bottom, a metal cathode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an indium tin oxide cathode, wherein the light emitting layer material is taken from any one of the seven-membered ring thermal activation delayed fluorescence materials of the present invention.
The seven-membered ring thermally activated delayed fluorescence material of the present invention and the preparation method and properties thereof are further explained by the following specific examples:
example 1
This example provides a seven-membered ring thermally activated delayed fluorescence material, and the synthetic route of compound 1 is as follows:
the synthesis method of the compound 1 specifically comprises the following steps:
synthesis of intermediate 1: a500 mL round-bottom flask was connected to a spherical condenser, dried, purged with nitrogen, and charged with raw material 1(2.52 g, 10mmol), raw material 2(2.47 g, 12mmol), palladium tetrakistriphenylphosphine (231.2 mg, 0.2mmol), 20mL of a 2mol/L aqueous solution of potassium carbonate, and 200mL of toluene, respectively. Reflux was heated for 24 h, cooled to room temperature, the solution was poured into water, extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate and then isolated on silica gel column to give intermediate 1(2.40 g, 72% yield).
Synthesis of intermediate 2: a200 mL round-bottom flask was connected to a spherical condenser, dried, purged with nitrogen, and added with intermediate 1(1.67 g, 5mmol), reduced iron powder (1.68 g, 30mmol), 3% ammonium chloride solution (5 mL), and toluene (100 mL). Reflux was carried out for 5 hours under heating, cooled to room temperature, filtered to give a filtrate, and concentrated by rotary evaporation and then isolated on silica gel column to give intermediate 2(1.47 g, 97% yield).
Synthesis of intermediate 3: a200 mL round-bottom flask was connected to a spherical condenser, dried, purged with nitrogen, and added with intermediate 2(3.04 g, 10mmol), potassium tert-butoxide (2.24 g, 20mmol), and 100mL of dimethyl sulfoxide, respectively. Reflux was carried out under heating for 12 hours, cooled to room temperature, quenched with ammonium nitrate solution, extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate and then separated on a silica gel column to obtain intermediate 3(2.25 g, yield 84%).
Synthesis of intermediate 4: a200 mL two-necked round-bottomed flask was placed in a spherical condenser, dried, purged with nitrogen, and added with intermediate 1(5.87 g, 22mmol), starting material 3(1.93 g, 10mmol), cesium carbonate (9.77 g, 30mmol), and 100mL of N, N-dimethylformamide, respectively. Heating to reflux for 24 h, cooling to room temperature, pouring the solution into water and filtering gave a white precipitate and recrystallization of the crude product from ethanol gave intermediate 2(5.23 g, 76% yield).
Synthesis of Compound 1: a100 mL Schlenk flask was charged with intermediate 2(3.44 g, 5mmol), 50mL t-butylbenzene, three times frozen in liquid nitrogen, 2.4mL n-butyllithium (6mmol,2.5mol/L n-hexane) slowly added at 0 deg.C, slowly heated to 60 deg.C and allowed to react for 4 hours. Cooled to-42 deg.C, boron tribromide (0.68mL, 7mmol) was added slowly and the reaction was allowed to warm slowly to room temperature for an additional 2 hours. N, N-diisopropylethylamine (1.65mL, 10mmol) was added slowly under ice-water bath and gradually heated to 120 ℃ for 24 hours. The reaction solution was cooled to room temperature, washed three times with a sodium acetate solution, the organic phase was collected and dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate 10/1 (vol.%)) to give compound 1(0.62 g, 20% yield).
Example 2
This example provides a seven-membered ring thermally activated delayed fluorescence material, and the synthetic route of compound 23 is as follows:
the synthesis method of the compound 23 specifically comprises the following steps:
synthesis of intermediate 5: a200 mL two-necked round-bottomed flask was placed in a spherical condenser, dried, purged with nitrogen, and added with intermediate 3(5.87 g, 22mmol), starting material 4(2.27 g, 10mmol), cesium carbonate (9.77 g, 30mmol), and 100mL of N, N-dimethylformamide, respectively. Heating to reflux for 24 h, cooling to room temperature, pouring the solution into water and filtering gave a white precipitate and recrystallization of the crude product from ethanol gave intermediate 5(5.86 g, 81% yield).
Synthesis of intermediate 6: a200 mL round-bottom flask was connected to a spherical condenser, dried, purged with nitrogen, and added with intermediate 3(3.61 g, 5mmol), starting material 5(3.78 g, 22mmol), palladium tetrakistriphenylphosphine (115.6 mg, 0.1mmol), 2mol/L aqueous potassium carbonate solution 10mL, 100mL tetrahydrofuran, respectively. Heating to reflux for 24 h, cooling to room temperature, pouring the solution into water and filtering gave a white precipitate and recrystallization of the crude product from ethanol gave intermediate 6(2.66 g, 69% yield).
Synthesis of compound 23: a100 mL Schlenk flask was charged with intermediate 6(3.85 g, 5mmol), 50mL t-butylbenzene, and liquid nitrogen freeze-extracted three times, 2.4mL n-butyllithium (6mmol,2.5mol/L n-hexane) was added slowly at 0 deg.C, and the reaction was continued for 4 hours while slowly heating to 60 deg.C. Cooled to-42 deg.C, boron tribromide (0.68mL, 7mmol) was added slowly and the reaction was allowed to warm slowly to room temperature for an additional 2 hours. N, N-diisopropylethylamine (1.65mL, 10mmol) was added slowly under ice-water bath and gradually heated to 120 ℃ for 24 hours. The reaction solution was cooled to room temperature, washed three times with a sodium acetate solution, the organic phase was collected and dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate 10/1 (vol.%)) to give compound 23(0.67 g, 18% yield).
Example 3
This example provides a seven-membered ring thermally activated delayed fluorescence material, and the synthetic route of compound 68 is shown below:
the synthesis method of the compound 68 specifically comprises the following steps:
synthesis of intermediate 10: the synthesis of intermediate 3 was identical except that starting material 7(3.89 g, 15mmol) was used as the starting material to give intermediate 10(1.90 g, 74% yield).
Synthesis of intermediate 11: the synthesis was identical to that of intermediate 5, except that intermediate 10(5.65 g, 22mmol) was used to give intermediate 11(5.62 g, 80% yield).
Synthesis of intermediate 12: the synthesis was identical to that of intermediate 6, except that intermediate 11(3.51 g, 5mmol) was used to give intermediate 12(2.33 g, 65% yield).
Synthesis of compound 68: the synthesis of compound 23 was identical except that intermediate 12(3.58 g, 5mmol) was used to give compound 68(0.83 g, 24% yield).
In view of the excellent light emitting properties and narrowed fluorescence emission spectrum of the seven-membered ring thermally activated delayed fluorescence material, the present invention provides an example of the material as an organic light emitting device.
Example 4
The invention provides an organic light-emitting device based on a seven-membered ring thermal activation delayed fluorescence material as a light-emitting layer, which is characterized in that a metal cathode 1, an electron injection layer 2, an electron transport layer 3, a light-emitting layer 4, a hole transport layer 5, a hole injection layer 6, an anode 7 and a glass substrate 8 are sequentially stacked from top to bottom as shown in figure 1. Wherein, preferably, the metal cathode 1 is selected from aluminum, the electron injection layer 2 is selected from lithium fluoride, and the electron transport layer 3 is selected from the following structure
Compound LET003 of (a); the light-emitting layer 4 is composed of a host material and a guest materialDoping, wherein the host material has the following structure
Compound mCBP of (1), compound 68 as guest material
The mass ratio of the doped host material to the doped guest material is 90: 10; the hole transport layer 5 is selected to have the following structure
The compound of (4) NPB; the hole injection layer 6 is selected to have the following structure
The compound of (1) HATCN; the anode 7 is indium tin oxide.
Example 5
An organic electroluminescent device is provided, which is different from the organic electroluminescent device provided in example 4 in that: the material of the luminescent layer is compound 1.
Example 6
An organic electroluminescent device is provided, which is different from the organic electroluminescent device provided in example 4 in that: the material of the light-emitting layer is compound 23.
The seven-membered ring thermal activation delayed fluorescence material prepared in this example 1 was subjected to a thermal stability test, and the result is shown in fig. 2, and it can be seen from fig. 2 that the decomposition temperature of the seven-membered ring thermal activation delayed fluorescence material is 415 degrees, which indicates that the seven-membered ring thermal activation delayed fluorescence material is excellent in thermal stability.
The emission spectrum of the seven-membered ring thermal activation delayed fluorescence material prepared in the embodiment 1 is tested, and the result is shown in fig. 3, and as can be seen from fig. 3, the emission spectrum of the seven-membered ring thermal activation delayed fluorescence material is only 28nm, which indicates that the seven-membered ring thermal activation delayed fluorescence material has the characteristic of narrow emission spectrum, and the material has good color purity.
In conclusion, the accumulation of materials can be effectively improved through the introduction of the seven-membered ring, the intermolecular triplet state quenching is reduced, the efficiency roll-off is reduced, the stability of the device is improved, and the service life of the device is prolonged; meanwhile, a unique boron-nitrogen multiple resonance structure is adopted to endow the material with a narrower fluorescence emission spectrum and a higher external quantum efficiency value.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A seven-membered ring thermal activation delayed fluorescence material is characterized in that the chemical structure general formula is as follows:
wherein Ar is1-Ar4Each independently selected from benzene, thiophene, furan, pyridine or substituted aryl or heteroaryl as described above, R1-R12Each independently selected from one of hydrogen, deuterium, cyano or alkyl chain, X is selected from hydrogen, deuterium, halogen, cyano, alkyl chain or benzene, thiophene, furan, carbazole, pyridine, quinoline, isoquinoline and substituted aryl or heteroaryl as described above.
2. The seven-membered ring thermally activated delayed fluorescence material of claim 1, wherein said X is one of the following groups:
3. A seven-membered ring thermally activated delayed fluorescence material as claimed in any of claims 1-2, wherein the seven-membered ring thermally activated delayed fluorescence material is one of the following chemical structural formulas:
4. a preparation method of a seven-membered ring thermal activation delayed fluorescence material is characterized by comprising the following steps:
dissolving raw material aromatic boric acid and halogenated aromatic groups in a first solvent to obtain a first intermediate product under a first preset reaction condition;
dissolving the first intermediate product in a first solvent, adding sufficient iron powder and a 3% ammonium chloride solution, heating and refluxing, pouring the solution into water, filtering to obtain a filtrate, performing rotary evaporation and concentration, and performing silica gel column separation to obtain a second intermediate product;
dissolving the second intermediate product in a second solvent to obtain a third intermediate product aromatic amine under a second preset reaction condition;
dissolving the third intermediate product aromatic amine and difluorobromobenzene in a third solvent, adding cesium carbonate, heating and refluxing for 24 hours, pouring the solution into water, filtering to obtain a white precipitate, and recrystallizing by using a fourth solvent to obtain a fourth intermediate product;
and after the fourth intermediate product reacts with N-butyllithium at a low temperature, adding boron tribromide to continuously react, adding N, N-diisopropylethylamine, and stirring to react to obtain the seven-membered ring thermal activation delayed fluorescence material.
5. The method for preparing a seven-membered ring thermally activated delayed fluorescence material according to claim 4, wherein the first solvent is toluene, the second solvent is dimethyl sulfoxide, the third solvent is N, N-dimethylformamide, and the fourth solvent is ethanol.
6. The method for preparing a seven-membered ring thermally activated delayed fluorescence material of claim 4, comprising the steps of:
dissolving the third intermediate product aromatic amine and 5-bromo-2-chloro-1, 3-difluorobenzene in a first solvent, adding cesium carbonate, heating and refluxing for 24 hours, pouring the solution into water, filtering to obtain a white precipitate, and recrystallizing by using a fourth solvent to obtain a fifth intermediate product;
a sixth intermediate product of a substituted or unsubstituted aryl or heteroaryl group and a third intermediate product dissolved in a first solvent under first predetermined reaction conditions;
and after the sixth intermediate product reacts with N-butyllithium at a low temperature, adding boron tribromide to continuously react, adding N, N-diisopropylethylamine, and stirring to react to obtain the seven-membered ring thermal activation delayed fluorescence material.
7. The method for preparing a seven-membered ring thermally activated delayed fluorescence material as claimed in claim 4 or 6, wherein the aromatic boronic acid is
The halogenated aromatic group is one of the following chemical structural formulas:
8. the method for preparing a seven-membered ring thermally activated delayed fluorescence material according to claim 4 or 6, wherein the first predetermined reaction condition is: the catalyst is 2mol percent of tetratriphenylphosphine palladium and 5 times of potassium carbonate equivalent; the reaction temperature is 100-110 ℃ and the reaction time is 24 hours.
9. The method for preparing a seven-membered ring thermally activated delayed fluorescence material according to claim 4 or 6, wherein the second predetermined reaction condition is: the catalyst is 2 times of equivalent of potassium tert-butoxide, the reaction temperature is 160 ℃, and the reaction time is 12 hours.
10. An organic light-emitting device, comprising a metal cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, and an indium tin oxide anode in sequence from top to bottom, wherein the light-emitting layer is made of the seven-membered ring thermal activation delayed fluorescence material according to any one of claims 1 to 3.
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| CN114149458A (en) * | 2021-11-29 | 2022-03-08 | 苏州大学 | B/N organic electroluminescent material and preparation method and application thereof |
| CN114195813A (en) * | 2021-12-30 | 2022-03-18 | 中国科学技术大学 | Boron-containing fused ring compound and electronic device |
| WO2022183900A1 (en) * | 2021-03-01 | 2022-09-09 | 北京大学深圳研究生院 | Organic light-emitting device having thermally activated delayed fluorescent material as light-emitting layer material |
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| CN111029477A (en) * | 2019-12-10 | 2020-04-17 | 昆山国显光电有限公司 | Organic electroluminescent device, display panel and display device |
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| WO2022183900A1 (en) * | 2021-03-01 | 2022-09-09 | 北京大学深圳研究生院 | Organic light-emitting device having thermally activated delayed fluorescent material as light-emitting layer material |
| EP4141012A1 (en) * | 2021-08-30 | 2023-03-01 | Samsung Electronics Co., Ltd. | Heterocyclic compound, organic light-emitting device including the heterocyclic compound, and electronic apparatus including the organic light-emitting device |
| CN114149458A (en) * | 2021-11-29 | 2022-03-08 | 苏州大学 | B/N organic electroluminescent material and preparation method and application thereof |
| CN114149458B (en) * | 2021-11-29 | 2023-01-06 | 苏州大学 | B/N organic electroluminescent material and preparation method and application thereof |
| CN114195813A (en) * | 2021-12-30 | 2022-03-18 | 中国科学技术大学 | Boron-containing fused ring compound and electronic device |
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