CN112940025A - Chiral thermal activation delayed fluorescent material, preparation method and application - Google Patents
Chiral thermal activation delayed fluorescent material, preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 230000003111 delayed effect Effects 0.000 title claims abstract description 34
- 238000007725 thermal activation Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 27
- -1 arylamine compounds Chemical class 0.000 claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- 239000000543 intermediate Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
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- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
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- 230000035484 reaction time Effects 0.000 claims description 8
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- 230000003472 neutralizing effect Effects 0.000 claims description 4
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
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- 238000013461 design Methods 0.000 abstract description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
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- 239000000047 product Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
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- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
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- CZNGTXVOZOWWKM-UHFFFAOYSA-N methyl 4-bromobenzoate Chemical compound COC(=O)C1=CC=C(Br)C=C1 CZNGTXVOZOWWKM-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- SPPLEVHTUMPNLQ-UHFFFAOYSA-N 10-[4-(4-carbazol-9-ylphenyl)sulfonylphenyl]-9,9-dimethylacridine Chemical compound C1=2C=CC=CC=2N(C2=C1C=CC=C2)C1=CC=C(S(=O)(=O)C2=CC=C(N3C4=CC=CC=C4C(C4=C3C=CC=C4)(C)C)C=C2)C=C1 SPPLEVHTUMPNLQ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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Abstract
The invention discloses a chiral thermal activation delayed fluorescent material, a preparation method and application. By molecular design, an axial chiral induction center, electron-withdrawing group borate and various arylamine compounds are introduced into molecules to synthesize the chiral thermal activation delay fluorescent material. The synthesized chiral thermal activation delayed fluorescence material has the advantages of cheap raw materials, higher synthesis yield, good stability, solubility and film forming property, high light-emitting asymmetric factor, high fluorescence quantum efficiency and the like, so the material has wide application value in the field of circular polarization organic electroluminescent devices.
Description
Technical Field
The invention relates to an organic photoelectric material, a preparation method and application, in particular to a chiral thermal activation delayed fluorescence material, a preparation method and application.
Background
The organic photoelectric material is an organic material with photoelectric activity, has low preparation cost, small processing difficulty, easy industrial production and quick photoelectric response, and is widely applied to the fields of organic light-emitting diodes, organic solar cells, organic thin-film transistors, organic memories, sensors and the like. Among them, the application of organic photoelectric materials to organic light emitting diodes OLEDs is one of the most promising technologies for lighting devices or screen displays. Organic compounds are used as luminescent dopants, are embedded in the electronic matrix, and emit light after electric excitation. Compared with a standard LCD, the OLED has smaller thickness, faster response time and higher contrast.
In contrast to lighting devices, displays require anti-glare filters to avoid external light sources from reflecting off their emitting surfaces (e.g., sunlight or public lighting). The most commonly used filters consist of a quarter-wave plate and a polarizer. However, this structure reduces the unpolarized light intensity emitted by a conventional OLED display by at least 50%. Therefore, by introducing a highly efficient circularly polarized light emitter, it is an important approach to increase efficiency while reducing power consumption of portable OLED displays. The high degree of polarization enables light emitted by the display to pass through the antiglare filter layer without any attenuation. Thus, combining the circularly polarized emitter with the thermally activated delayed phosphor opens up a new field of emissive dopants for next generation display applications. The good chiral thermal activation delayed fluorescence molecule should have high photoluminescence quantum yield, small singlet-triplet energy gap and large luminescence asymmetry factor, thereby effectively realizing thermal activation delayed fluorescence property and circular polarization luminescence property.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a chiral thermal activation delayed fluorescent material.
The invention aims to provide a preparation method and application of the chiral thermal activation delayed fluorescent material.
Through molecular design, an axial chiral induction center, electron-withdrawing group borate and various electron donor groups are introduced into molecules to synthesize the heat-activated delayed fluorescent material with circular polarization luminescence. The invention provides a novel method for preparing a chiral thermal activation delayed fluorescent material, and the synthesized chiral thermal activation delayed fluorescent material has the advantages of cheap raw materials, higher synthesis yield, good stability, solubility and film-forming property, high luminescent asymmetry factor, higher fluorescence quantum efficiency and the like, so the material has wide application value in the field of circular polarization organic electroluminescent devices.
The technical scheme is as follows: the invention provides a chiral thermal activation delayed fluorescent material, which has a molecular structure general formula shown in formula (I):
wherein R is1、R2、R3、R4、R5Respectively hydrogen or arylamine compounds.
Further, the arylamine compound is selected from one of the following groups:
further, according to different chiral configurations, the general formula of the molecular structure is divided into an S configuration and an R configuration as shown in the following formula (I):
further, all molecular chiral configurations are shown in S configuration for either:
further, the preparation method of the chiral thermal activation delayed fluorescence material comprises the following steps:
(1) adding raw material 1-1, raw material 1-2 or raw material 1-3 and alkali into organic solvent under inert gas atmosphere, stirring, heating and refluxing for reaction, adding raw material 2-1, raw material 2-2 or raw material 2-3 into organic solvent under inert gas atmosphere, stirring for dissolvingThen heating reflux reaction is continued, after the reaction is finished, pouring into ice water, neutralizing with acid, precipitating, recrystallizing and purifying to prepare the following formula A1、A2、A3Any one of the intermediates:
(2) adding any intermediate, arylamine compound, alkali and catalyst in the step (1) into an organic solvent under the atmosphere of inert gas, stirring uniformly, heating for reflux reaction, cooling to room temperature after the reaction is finished, adding water for quenching, extracting, and purifying by column chromatography to obtain the compound shown in the formula B1、B2、B3、B4、B5、B6、B7、B8、B9、B10、B11、B12、B13、B14、B15、B16、B17、B18Any one of the intermediates;
(3) adding an organic solvent into any intermediate in the step (2) in an inert gas atmosphere, uniformly stirring, injecting a catalyst, reacting at room temperature, adding water for quenching after the reaction is finished, extracting, and purifying by column chromatography to obtain the compound C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18Any one of the intermediates;
(4) putting any intermediate in the step (3) and R/S-binaphthol in an inert gas atmosphereAdding organic solvent under the condition of surrounding, uniformly stirring, injecting catalyst, reacting at room temperature, adding water for quenching after the reaction is finished, extracting, and purifying by column chromatography to obtain the formula M-S1、M-S2、M-S3、M-S4、M-S5、M-S6、M-S7、M-S8、M-S9、M-S10、M-S11、M-S12、M-S13、M-S14、M-S15、M-S16、M-S17、M-S18All the molecular chiral configurations are shown in S configuration.
Further, in the step (1), the dosage ratio of the raw material 1-1 to the raw material 2-1 or the raw material 1-2 to the raw material 2-2 or the raw material 1-3 to the raw material 2-3 is 1.2: 1-1.5: 1; the heating temperature is 40-60 ℃; the reaction time is 8-12 hours.
Further, the reaction conditions in the step (2) are as follows:
the dosage of the arylamine compound is the intermediate A1、A2Or A32.5-5 times of the dosage;
the heating temperature is 90-120 ℃;
the alkali is any one of cesium carbonate or sodium tert-butoxide, and the dosage is the intermediate A1、A2Or A32.5-3 times of the dosage;
the catalyst is palladium acetate and tri (tert-butyl) phosphine tetrafluoroborate, and the dosage of the palladium acetate and the tri (tert-butyl) phosphine tetrafluoroborate are respectively an intermediate A1、A2Or A30.05-0.10 and 0.15-0.20 times of the dosage;
the organic solvent is toluene; the reaction time is 12-36 hours; the eluent is dichloromethane/petroleum ether, and the volume is 1: 3-1: 2.
Further, the reaction conditions in the step (3) are specifically as follows:
the catalyst adopts boron trifluoride diethyl etherate complex, and the dosage of the boron trifluoride diethyl etherate complex is the intermediate A1、A2Or A32-3 times of the total weight of the composition;
the organic solvent is anhydrous dichloromethane;
the reaction time is 0.5-2 hours;
the eluent is dichloromethane/petroleum ether with the volume of 1: 5-1: 3.
The reaction conditions in the step (4) are as follows:
the dosage of the R/S-binaphthol is the intermediate C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17Or C183-6 times of the total weight of the composition;
the catalyst adopts diethyl aluminum monochloride, and the dosage is the intermediate A1、A2Or A31.5 to 2.0 times of;
the organic solvent is anhydrous dichloromethane;
the reaction time is 20-60 minutes;
the eluent is dichloromethane/petroleum ether with the volume of 1: 6-1: 5.
The chiral thermal activation delayed fluorescence material is applied to an organic light-emitting diode.
Has the advantages that:
(1) the chiral thermal activation delayed fluorescence material of the invention introduces axial chiral binaphthyl as a chiral induction center, and realizes stable chiral transfer.
(2) The chiral thermal activation delayed fluorescence material is an organic micromolecular material, and has good solubility and film forming property, high thermal stability and structural stability.
(3) The chiral thermal activation delayed fluorescent material of the invention is used as a light-emitting layer guest material to be applied to an organic light-emitting diode to obtain a better effect, thereby realizing the circular polarization light-emitting organic light-emitting diode and widening the range of the field of organic photoelectric materials.
(4) The preparation method of the chiral thermal activation delayed fluorescent material is simple, the raw materials are cheap, and the synthesis yield is high.
(5) The chiral thermal activation delayed fluorescence material can adjust the development of the luminescent color of the material to near infrared by changing the type and the number of connected arylamine compounds, thereby realizing the emission of the near infrared light.
Drawings
FIG. 1 is an absorption emission diagram comprising example 1 in a dichloromethane solution;
FIG. 2 is a low temperature singlet and triplet state test pattern comprising example 1;
FIG. 3 is a transient decay curve comprising the doped film of example 1;
FIG. 4 is a photo circularly polarized spectrum comprising the neat film of example 1;
fig. 5 is an electric circularly polarized spectrum including the organic light emitting diode of example 1.
Detailed Description
Example 1
The structural formula of the target product is as follows:
synthesis of chiral thermal activation delayed fluorescent material:
Step 3, 2.0g of intermediate B1Dissolving with 30mL of anhydrous dichloromethane under the protection of inert atmosphere, adding 2.2mL of boron trifluoride diethyl etherate, stirring at normal temperature overnight, extracting, purifying by column chromatography, wherein the eluent is dichloromethane/petroleum ether at a ratio of 1: 3 to obtain intermediate C1Yield 74%.1H NMR(400MHz，DMSO-d6)：δ＝8.14(d，J＝8.0Hz，4H)，7.46(t，J＝16Hz，9H)，7.31-7.25(m，J＝24Hz，12H)，6.89(d，J＝12Hz，4H)。13C NMR(100MHz，CDCl3)：δ＝178.92，153.63，145.74，130.42，129.83，126.49，125.56，123.44，118.92，90.98。
Example 2
The structural formula of the target product is as follows:
synthesis of chiral thermal activation delayed fluorescent material:
Step 3, 2g of intermediate product B2Dissolving with 30mL of anhydrous dichloromethane under the protection of inert atmosphere, adding 2.2mL of boron trifluoride diethyl etherate, stirring at normal temperature overnight, extracting, purifying by column chromatography, wherein the eluent is dichloromethane/petroleum ether at a ratio of 1: 3 to obtain intermediate C2The yield was 65%.1H NMR(400MHz，DMSO-d6)：δ＝8.55(d，J＝8.0Hz，4H)，8.30(d，J＝8.0Hz，4H)，7.91(d，J＝8Hz，4H)，7.57(d，J＝8Hz，4H)，7.49(t，J＝16Hz，4H)，7.35(t，J＝16Hz，4H)，7.64(s，1H)。13C NMR(100MHz，CDCl3)：δ＝181.80，144.51，139.82，130.84，129.83，126.58，126.47，124.28，121.24，120.64，109.86，93.42。
Each intermediate in the above embodiments can be replaced according to actual needs, so as to obtain the corresponding target product.
Example 3
The structure of a doped universal device prepared by taking the compound as a guest material is as follows:
ITO/PEDOT：PSS(70nm)/CzAcSF：10wt％emitter(40nm)/DPEPO(10nm)/TmPyPB(50nm)/Liq(1nm)/Al(100nm)
wherein, ITO and Al are respectively used as an anode and a cathode; PEDOT: PSS and Liq are respectively used as a hole injection layer and an electron injection layer; DPEPO as exciton blocking layer; TmPyPB acts as a hole blocking and electron transport layer.
The solution processed chiral thermally activated delayed fluorescence organic light emitting diode was prepared as follows:
all the above materials were used as received without further purification. The device is prepared by the following steps: and ultrasonically cleaning the ITO glass substrate by using an ITO cleaning agent, deionized water, acetone and ethanol for 30 minutes respectively, and then drying the ITO glass substrate for more than one hour at the temperature of 120 ℃ in a vacuum oven. After 15 minutes of uv-ozone treatment, 30nm PEDOT: PSS was spin coated on an ITO substrate and dried in a glove box at 120 ℃ for 10 minutes. Then, chlorobenzene (10mg mL)-1) Spin coating the light emitting layer to PEDOT: PSS, and annealed using a hot plate at 50 ℃ for 10 minutes. Thereafter, the sample was transferred to a thermal evaporation chamber at 5X 10-4DPEPO (10nm), TmPyPB (50nm), Liq (1nm) and Al (100nm) were deposited by thermal evaporation under Pa. And finally, carrying out UV curing packaging, and baking for 60min at 80 ℃.
TABLE 1. comprising compoundsThing M1Test results of organic light emitting diode device Performance
And (4) surface note: lambda [ alpha ]ELIs the maximum emission wavelength in the electroluminescence spectrum of the device; vonThe turn-on voltage of the device; l ismaxIs the maximum brightness of the device; CE is the maximum current efficiency of the device; PE is the maximum power efficiency of the device; EQE is the maximum external quantum efficiency.
Claims (10)
1. A chiral thermal activation delayed fluorescence material has a molecular structure general formula shown in formula (I):
wherein R is1、R2、R3、R4、R5Respectively hydrogen or arylamine compounds.
2. The chiral thermally activated delayed fluorescence material of claim 1, wherein: the arylamine compound is selected from one of the following groups:
3. the chiral thermally activated delayed fluorescence material of claim 1, wherein: according to different chiral configurations, the general formula of the molecular structure is as shown in formula (I) and is divided into S configuration and R configuration as follows:
4. the chiral thermally activated delayed fluorescence material according to any of claims 1-3, wherein: all molecular chiral configurations are shown in S configuration for either:
5. the method for preparing a chiral thermally activated delayed fluorescence material according to any of claims 1-4, wherein: the method comprises the following steps:
(1) adding organic solvent into raw material 1-1, raw material 1-2 or raw material 1-3 and alkali under inert gas atmosphere, stirring, heating for reflux reaction, adding organic solvent into raw material 2-1, raw material 2-2 or raw material 2-3 under inert gas atmosphere, stirring for dissolving, heating for reflux reaction, pouring into ice water, neutralizing with acid, precipitating, recrystallizing, and purifying to obtain the following formula A1、A2、A3Any one of the intermediates:
(2) adding any intermediate, arylamine compound, alkali and catalyst in the step (1) into an organic solvent under the atmosphere of inert gas, stirring uniformly, heating for reflux reaction, cooling to room temperature after the reaction is finished, adding water for quenching, extracting, and purifying by column chromatography to obtain the compound shown in the formula B1、B2、B3、B4、B5、B6、B7、B8、B9、B10、B11、B12、B13、B14、B15、B16、B17、B18Any one of the intermediates;
(3) adding an organic solvent into any intermediate in the step (2) in an inert gas atmosphere, uniformly stirring, injecting a catalyst, reacting at room temperature, adding water for quenching after the reaction is finished, extracting, and purifying by column chromatography to obtain the compound C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18Any one of the intermediates;
(4) adding an organic solvent into any intermediate and R/S-binaphthol in the step (3) under the inert gas atmosphere, uniformly stirring, injecting a catalyst, reacting at room temperature, adding water for quenching after the reaction is finished, extracting, and purifying by column chromatography to obtain the M-S1、M-S2、M-S3、M-S4、M-S5、M-S6、M-S7、M-S8、M-S9、M-S10、M-S11、M-S12、M-S13、M-S14、M-S15、M-S16、M-S17、M-S18All the molecular chiral configurations are shown in S configuration.
6. The method for preparing the chiral thermally activated delayed fluorescence material according to claim 5, wherein: in the step (1), the dosage ratio of the raw material 1-1 to the raw material 2-1 or the raw material 1-2 to the raw material 2-2 or the raw material 1-3 to the raw material 2-3 is 1.2: 1-1.5: 1; the heating temperature is 40-60 ℃; the reaction time is 8-12 hours.
7. The method for preparing the chiral thermally activated delayed fluorescence material according to claim 5, wherein: the reaction conditions in the step (2) are as follows:
the dosage of the arylamine compound is the intermediate A1、A2Or A32.5-5 times of the dosage;
the heating temperature is 90-120 ℃;
the alkali is any one of cesium carbonate or sodium tert-butoxide, and the dosage is the intermediate A1、A2Or A32.5-3 times of the dosage;
the catalyst is palladium acetate and tri (tert-butyl) phosphine tetrafluoroborate, and the dosage of the palladium acetate and the tri (tert-butyl) phosphine tetrafluoroborate are respectively an intermediate A1、A2Or A30.05-0.10 and 0.15-0.20 times of the dosage;
the organic solvent is toluene; the reaction time is 12-36 hours; the eluent is dichloromethane/petroleum ether, and the volume is 1: 3-1: 2.
8. The method for preparing the chiral thermally activated delayed fluorescence material according to claim 5, wherein: the reaction conditions in the step (3) are specifically as follows:
the catalyst adopts boron trifluoride diethyl etherate complex, and the dosage of the boron trifluoride diethyl etherate complex is the intermediate A1、A2Or A32-3 times of the total weight of the composition;
the organic solvent is anhydrous dichloromethane;
the reaction time is 0.5-2 hours;
the eluent is dichloromethane/petroleum ether with the volume of 1: 5-1: 3.
9. The method for preparing the chiral thermally activated delayed fluorescence material according to claim 5, wherein: the reaction conditions in the step (4) are as follows:
the dosage of the R/S-binaphthol is the intermediate C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17Or C183-6 times of the total weight of the composition;
the catalyst adopts diethyl aluminum monochloride, and the dosage is the intermediate A1、A2Or A31.5 to 2.0 times of;
the organic solvent is anhydrous dichloromethane;
the reaction time is 20-60 minutes;
the eluent is dichloromethane/petroleum ether with the volume of 1: 6-1: 5.
10. Use of the manually thermally activated delayed fluorescence material of claim 1 in an organic electroluminescent diode.
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