CN110759935A - Blue thermal activity delayed fluorescent material based on fluorine boron complex and application thereof - Google Patents
Blue thermal activity delayed fluorescent material based on fluorine boron complex and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 41
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- 239000002019 doping agent Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
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- 239000000243 solution Substances 0.000 description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- JSEQNGYLWKBMJI-UHFFFAOYSA-N 9,9-dimethyl-10h-acridine Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3NC2=C1 JSEQNGYLWKBMJI-UHFFFAOYSA-N 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
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- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical compound F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000001194 electroluminescence spectrum Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- DENKGPBHLYFNGK-UHFFFAOYSA-N 4-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Br)C=C1 DENKGPBHLYFNGK-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
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- 238000004440 column chromatography Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- OTVZGAXESBAAQQ-UHFFFAOYSA-N pyrazine-2,3-dicarbonitrile Chemical compound N#CC1=NC=CN=C1C#N OTVZGAXESBAAQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 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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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
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Abstract
The invention discloses a receptor-donor type (A) based on a fluoroboric complex1‑A2-D) and its use. By introducing boron atoms into molecules to construct a boron-fluorine complex, the energy level difference between a singlet state and a triplet state of the molecules can be effectively reduced, the reverse system crossing rate of the molecules is increased, and the luminous efficiency of the material is further enhanced. The material is used as a dopant of a luminescent layer, and an organic electroluminescent device is prepared by a solution method, so that the maximum external quantum efficiency of up to 20.1 percent is obtained. The molecule is simple and efficient, and provides a research idea for designing efficient blue TADF materials.
Description
Technical Field
The invention relates to an organic Thermal Activity Delayed Fluorescence (TADF) material containing a fluorine boron complex, in particular to a blue thermal activity delayed fluorescence material taking a fluorine boron unit and a 1,3, 4-oxadiazole unit as a double receptor and 9, 9-dimethylacridine as a donor, and an application thereof as a light-emitting layer material of an organic electroluminescent diode, belonging to the technical field of organic electroluminescent materials.
Technical Field
Since the first report of pure organic Thermally Active Delayed Fluorescence (TADF) as a dopant for a light emitting layer of organic electroluminescent diodes (OLEDs) by the Adachi project group in 2012, TADF materials have attracted extensive attention of researchers. The thermally active delayed fluorescent material can excite triplet state by reverse intersystem crossingSon (S)1) Conversion into singlet excitons (T)1) Followed by luminescence by radiative transition. Compared with traditional phosphorescent materials containing noble metals (such as Pt and Ir), the TADF material does not need noble metals and can theoretically achieve 100% internal quantum efficiency, which is beneficial to reducing cost and protecting environment.
In general, S1And T1With a small energy gap difference (Delta E)ST) The rate of reverse intersystem crossing can be increased, thereby imparting TADF properties to the material. Based on this concept, the TADF materials have made a significant substantial progress from blue to red light over the last few years. Currently, the research on TADF molecules has focused mainly on twisted donor-acceptor frameworks. The structure can effectively realize the separation of the energy levels of the highest occupied orbit and the lowest vacant orbit, thereby obtaining smaller Delta EST. In these TADF molecules, commonly used donors are diphenylamine, carbazole, acridine, phenoxazine, etc. units; and diphenyl sulfone, benzophenone, triazine, pyrazine-2, 3-dinitrile, cyano and the like as the main acceptor. Although TADF materials have met with great success over the past few years, there are still scientific issues that need to be addressed, such as lack of acceptor building blocks, roll-off in device efficiency based on TADF materials, and the like.
Boron difluoride (BF)2) Complexes are of particular interest in organic semiconductors due to their excellent electron accepting ability, higher extinction coefficients in solutions and solids, and luminous efficiency. However, based on BF2The use of dyes in OLEDs has been rarely reported, let alone in TADF-OLEDs. To our knowledge, only a few reports are currently made based on BF2The TADF material of (1). However, these reports are based on BF2And its efficiency is generally low, with a maximum external quantum efficiency of typically around 10%. Thus, BF-based is obtained2Chromophore based blue TADF materials and how to improve BF2The device efficiency of the chromophore TADF material is worth further exploration, which has important research significance for expanding the blue TADF material.
Disclosure of Invention
The invention aims to provide a high-efficiency blue thermal activity delayed fluorescence material which takes a boron-fluorine unit and a 1,3, 4-oxadiazole unit as double receptors and 9, 9-dimethylacridine as donors.
Another object of the present invention is to provide an application of a blue thermal activity delayed fluorescence material as a material of a light emitting layer of an organic electroluminescent diode, which can obtain an organic electroluminescent device with excellent light emitting performance.
In order to achieve the technical purpose, the invention provides a thermal activity delayed fluorescence material based on a fluorine boron complex, which has a structure of formula 1-formula 4:
the receptor-donor (A) of the formulas 1 to 4, which uses a fluorine boron unit and a 1,3, 4-oxadiazole unit as double receptors and 9, 9-dimethylacridine as donors1-A2-D) type thermally active delayed fluorescent material. The structure is beneficial to adjusting the energy level difference between the singlet state and the triplet state of the molecule, and the reverse system crossing rate of the material is increased, so that the luminous performance of the material is improved.
The invention also provides application of the acceptor-donor type thermal activity delayed fluorescent material, and the acceptor-donor type thermal activity delayed fluorescent material is used as a luminescent layer material of an organic electroluminescent diode and is used for an organic electroluminescent device. The device obtains the maximum external quantum efficiency of 20.1 percent
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
the construction principle of the thermal activity delayed fluorescent material is basically a donor-acceptor type structure, the invention firstly takes a boron-fluorine unit as an electron acceptor in a molecule and introduces the acceptor-donor type thermal activity delayed fluorescence with a double acceptor unit. The thought is more favorable for adjusting the energy level difference between the singlet state and the triplet state of the molecule, and the reverse system crossing rate of the material is increased, so that the luminous performance of the material is improved.
The invention uses the thermal activity delay fluorescent material with receptor-donor type as the luminescent layer material of the organic electroluminescent diode, and obtains the maximum external quantum efficiency of 20.1%. Compared with acceptor-donor type fluorine boron derivatives, the acceptor-donor type fluorine boron complex materials have better external quantum efficiency and bluer luminescent color.
Drawings
FIG. 1 is a diagram showing UV-visible absorption and photoluminescence spectra of OH-OXD and BF-OXD compounds prepared in example 1 of the present invention in toluene.
FIG. 2 is a diagram of the UV-VIS absorption spectra of the compound OH-OXD prepared in example 1 of the present invention in different solvents.
FIG. 3 is a diagram of the UV-visible absorption spectra of the compound BF-OXD prepared in example 1 of the present invention in different solvents.
FIG. 4 is a photoluminescence chart of the compound OH-OXD prepared in example 1 of the present invention in different solvents.
FIG. 5 is a photoluminescence chart of the compound BF-OXD prepared in example 1 in different solvents.
FIG. 6 shows electroluminescence spectra of OH-OXD and BF-OXD compounds obtained in example 1 of the present invention.
FIG. 7 is a graph showing the external quantum efficiency of OH-OXD and BF-OXD compounds prepared in example 1.
Detailed Description
The following specific examples are intended to further illustrate the invention, but these specific embodiments do not limit the scope of the invention in any way.
Example 1
The preparation methods of formula 1-formula 4 are described by taking OHOXD and BFOXD as examples
Synthesis of Compound 1
4-bromobenzoyl chloride (14.4g,66.0mmol), triethylamine (6.7g,66.0mmol), 80mL of dry dichloromethane were added to a 500mL three-necked flask, stirred at room temperature under nitrogen, and then dissolved in 80mL of dry dichloromethaneSalicyloyl hydrazine (10g,66mmol) was added dropwise to the reaction and the mixture was stirred at room temperature overnight. After the reaction is stopped, pouring the mixture into distilled water, separating out a precipitate, performing suction filtration, and recrystallizing filter residues by using absolute ethyl alcohol to obtain 13g of a white intermediate. The intermediate was then poured into 50mL of phosphorus oxychloride solution and reacted at reflux for 12 h. And cooling the reaction liquid to room temperature, pouring the reaction liquid into ice water, separating out a precipitate, performing suction filtration, and recrystallizing the filter residue by using absolute ethyl alcohol to obtain 9.5g of white solid with the yield of 46%.1H NMR(300MHz,CDCl3)δ10.13(s,1H),8.04-7.99(m,2H),7.85(dd,J＝1.5Hz,6.6Hz,1H),7.72-7.69(m,2H),7.50-7.44(m,1H), 7.15(dd,J＝0.9Hz,7.5Hz,1H),7.07-7.02(m,1H).13C NMR(100MHz,CDCl3)δ 164.32,162.52,157.68,133.85,132.55,128.36,126.89,126.46,122.14,119.95, 117.66,107.86.
Synthesis of compound OH-OXD
To a 100mL single-neck flask were added compound 1(1.00g,2.24mmol), 9-dimethylacridine (499mg,2.47mmol), sodium tert-butoxide (0.863g,8.98mmol), tris (dibenzylideneacetone) dipalladium (62mg, 0.067mmol), tri-tert-butylphosphine (27mg,0.13mmol), and 60mL of toluene in this order, and the mixture was reacted at 110 ℃ for 24h under nitrogen. After the reaction is stopped, cooling the reaction solution to room temperature, extracting with dichloromethane (3X 30mL), collecting an organic layer, and sequentially washing the organic layer with water (50mL), drying, and distilling under reduced pressure to remove the solvent; the residue was purified by petroleum ether: column chromatography with dichloromethane (V: V ═ 2:1) as eluent gave 430mg of white solid in 43% yield.1H NMR(300MHz,CDCl3)δ10.20(s,1H),8.44-8.40(m,2H),7.91(dd, J＝1.5Hz,6.6Hz,1H),7.59-7.46(m,5H),7.19(dd,J＝0.6Hz,7.8Hz,1H),7.10-6.95(m,5H),6.34-6.31(m,2H),1.71(s,6H).13C NMR(100MHz,CDCl3)δ 164.47,162.75,157.78,145.18,140.40,133.88,132.05,130.61,129.65,126.53, 126.45,125.41,122.87,121.74,120.02,117.73,114.20,107.99,36.06,31.13.HRMS (ESI)m/zcalcd.for C29H24N3O2,446.186260[M+H]+；found:446.18626.
Synthesis of compound BF-OXD
To a 100mL two-necked flask were added OH-OXD (2g,4.49mmol) and anhydrous triethylamine (500 m)g,4.93mmol) and 50mL of dry dichloromethane, stirring at room temperature under the protection of nitrogen, then dropwise adding boron trifluoride diethyl etherate (1.96g,13.47mmol) into the reaction solution, and stirring at room temperature overnight after dropwise adding. After the reaction was complete, the precipitate was filtered off and recrystallized from ethanol to give 1.86g of a yellow solid in 84% yield.1H NMR(400MHz,CDCl3)δ8.39(d,J＝8.0Hz,2H),7.87(dd,J＝1.6Hz,6.4Hz,1H), 7.73-7.68(m,1H),7.63(d,J＝7.2Hz,2H),7.51(d,J＝8.0Hz,2H),7.29(d,J＝8.4 Hz,1H),7.14(t,J＝7.6Hz,1H),7.08-7.00(m,4H),6.45(d,J＝7.6Hz,2H),1.68(s, 6H).19F NMR(282MHz,CDCl3)δ136.45.HR-MS(ESI):m/zcalcd.for C29H23BF2N3O2,494.184581[M+H]+；found:494.185103.
Example 2
Uv-vis absorption spectroscopy test of compounds OHOXD and BFOXD in example 1.
Respectively dissolving OH-OXD and BF-OXD in toluene to prepare 10-5And M, testing the ultraviolet visible absorption spectrum of the solution. As can be seen from fig. 1, the ultraviolet-visible absorption spectrum of compounds OHOXD and BFOXD in solution has roughly two absorption peaks: the absorption peak at short wavelengths (350nm) is mainly attributed to the transition absorption of pi-pi of the molecule; the absorption peak of long wavelength (> 350nm) is attributed to the charge transfer (ICT) transition absorption peak from donor unit to acceptor unit in the molecule.
Example 3
Photoluminescence testing of the compounds OHOXD and BFOXD of example 1. Dissolving OOHXD and BFOXD in toluene to obtain 10-5M solution, the solution of which was tested for photoluminescence spectra as shown in figure 1.
As can be seen from the figure, under the excitation of light, the maximum emission peak of the compounds OHOXD and BFOXD in the toluene solution is 472nm, and blue-green light emission is presented. Also, both compounds OHOXD and BFOXD showed a change in the wavelength of the emitted light in different solvents (fig. 4 and 5): as the polarity of the solvent increased, the luminescence color gradually red-shifted, indicating that the compounds OHOXD and BFOXD have larger intramolecular charge transfer.
Example 4
The compounds OHOXD and BFOXD are used as dopants of a light emitting layer of a device to prepare an organic electroluminescent diode with the structure of ITO/PEDOT: PSS (40nm)/CZAcSF: OHOXD (or BFOXD) (90:10,50nm)/DPEPO (10nm)/TmPyPB (50nm)/Liq (1nm)/Al (100 nm). PSS is a hole injection layer, CZAcSF is a main body material of a light-emitting layer, DPEPO is a hole blocking layer, TmPyPB is an electron transport layer, and Liq/Al is a cathode. The electroluminescence spectrum of the device is shown in fig. 6; where the maximum external quantum efficiency of the BFOXD-based device was obtained to be 20.1%, as shown in figure 7.
While the present invention has been described in connection with the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. In light of the present inventive concept, those skilled in the art will recognize that certain changes may be made in the embodiments of the invention to which the invention pertains without departing from the spirit and scope of the claims.
Claims (3)
1. 4 kinds of thermal activity delay fluorescent materials based on the fluorine boron complex are constructed, which is characterized in that: has the structure of formula 1-4:
2. the thermally activated delayed fluorescence material of formula 1 to formula 4 according to claim 1, wherein: the compound has the following formula 1-formula 4, and has an acceptor-donor type framework, which is constructed by Ullmann coupling and complex reaction.
3. Use of the acceptor-donor type thermally active delayed fluorescent material according to claim 1 or 2, characterized in that: the blue light guest material is used for organic electroluminescent devices, and the maximum external quantum efficiency is as high as 20.1%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113078278A (en) * | 2021-03-26 | 2021-07-06 | 常州大学 | Application of solution-processable thermal activity delay fluorescent material in blue light device and hybrid white light device |
| CN113234098A (en) * | 2021-05-19 | 2021-08-10 | 浙江虹舞科技有限公司 | Organic light-emitting or thermal-induced delayed fluorescent material containing nitrogen difluoride-boron-oxygen heterocyclic acceptor and application thereof |
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| C. ADACHI等: "Boron difluoride hemicurcuminoid as an efficient far red to near-infrared emitter: toward OLEDs and laser dyes", 《CHEMICAL COMMUNICATIONS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113078278A (en) * | 2021-03-26 | 2021-07-06 | 常州大学 | Application of solution-processable thermal activity delay fluorescent material in blue light device and hybrid white light device |
| CN113078278B (en) * | 2021-03-26 | 2024-04-30 | 常州大学 | Use of solution processable thermally active delayed fluorescent materials in blue light devices and in hybrid white light devices |
| CN113234098A (en) * | 2021-05-19 | 2021-08-10 | 浙江虹舞科技有限公司 | Organic light-emitting or thermal-induced delayed fluorescent material containing nitrogen difluoride-boron-oxygen heterocyclic acceptor and application thereof |
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