CN113321660A - Multifunctional delayed fluorescent material and preparation method thereof - Google Patents

Multifunctional delayed fluorescent material and preparation method thereof Download PDF

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CN113321660A
CN113321660A CN202110580597.1A CN202110580597A CN113321660A CN 113321660 A CN113321660 A CN 113321660A CN 202110580597 A CN202110580597 A CN 202110580597A CN 113321660 A CN113321660 A CN 113321660A
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multifunctional
fluorescent material
delayed fluorescent
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樊嘉政
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Guangzhou All Things Internet Of Things Technology Co ltd
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Abstract

The invention belongs to the technical field of photoelectric display devices, and particularly relates to a multifunctional delayed fluorescent material and a preparation method thereof. The invention provides a multifunctional delayed fluorescent material, which has a structure shown in a formula (I): the invention also provides a preparation method of the multifunctional delayed fluorescent material, which comprises the steps of reacting the compound shown in the formula (II) with dibenzoquinoxaline-2, 3-dicarbonitrile to prepare the compound shown in the formula (I); the invention provides a multifunctional delayed fluorescent material and a preparation method thereof, and solves the technical problems that the existing TADF micromolecule red light material is low in efficiency and easy to generate aggregation quenching luminescence effect.

Description

Multifunctional delayed fluorescent material and preparation method thereof
Technical Field
The invention belongs to the technical field of photoelectric display devices, and particularly relates to a multifunctional delayed fluorescent material and a preparation method thereof.
Background
In recent years, due to the low efficiency of conventional fluorescent organic light emitting diodes and the high cost of phosphorescent organic light emitting diodes, scientists have been interested in developing a new generation of delayed organic electroluminescent materials based on the conversion of triplet excitons into singlet excitons, such as novel organic electroluminescent materials having a triplet-triplet delayed fluorescence effect and a thermally activated delayed fluorescence effect. Among them, TADF materials are the fastest growing. In the existing TADF material, the current TADF small molecule red light device has to break through in the aspects of turn-on voltage, maximum external quantum efficiency, efficiency attenuation and the like, and the device structure is relatively complex. In addition, in the existing electroluminescent material, strong pi-pi stacking interaction can be formed between luminescent molecules in an aggregation state, which can induce and generate strong intermolecular electron or energy transfer, H-aggregates or excimers and other processes or species which are not beneficial to luminescence, and promote excited state molecules to be mostly attenuated to a ground state in a non-radiative transition manner, thereby causing an aggregation quenching luminescence effect.
Therefore, the efficiency of the existing TADF small-molecule red light material is not high, and the aggregation quenching luminescence effect is easy to generate, which is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention provides a multifunctional delayed fluorescent material and a preparation method thereof, and solves the technical problems that the existing TADF micromolecule red light material is low in efficiency and easy to generate aggregation quenching luminescence effect.
The invention provides a multifunctional delayed fluorescent material, which has a structure shown in a formula (I):
Figure BDA0003085969760000021
the invention also provides a preparation method of the multifunctional delayed fluorescent material, which comprises the steps of reacting the compound shown in the formula (II) with dibenzoquinoxaline-2, 3-dicarbonitrile to prepare the compound shown in the formula (I);
Figure BDA0003085969760000022
preferably, the compound represented by the formula (II) is prepared by the following steps:
step 1: reacting a compound shown in a formula (V) with liquid bromine to obtain a compound shown in a formula (IV);
Figure BDA0003085969760000023
step 2: reacting the compound shown in the formula (IV) with 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane to obtain a compound shown in a formula (III);
Figure BDA0003085969760000031
and step 3: reacting the compound shown in the formula (III) with NBS to obtain the compound shown in the formula (II).
The invention has the following beneficial effects:
according to the embodiment of the invention, nitrile is introduced into dibenzoquinoxaline to be used as an acceptor, and the nitrile and a compound shown in a formula (II) form an A-D-A effect, so that an intramolecular charge transfer effect is improved, and further, an ICT phenomenon occurs to cause spectral red shift, and the prepared compound is positioned in a red light region and is a typical red light material. In addition, the embodiment of the invention forms an effective A-D-A effect, so that the carrier transmission efficiency is enhanced, the external quantum efficiency is effectively improved to more than 10%, and the typical delayed fluorescence effect is achieved. The compounds prepared in the examples of the present invention showed a rapid increase in luminescence intensity in THF/water mixtures of different water contents with no increase in water content, indicating that the compounds prepared in the present invention have typical AIE properties.
Drawings
FIG. 1 is a PL photoluminescence spectrum of example 5 of the present invention and comparative example 1;
FIG. 2 is a graph of external quantum efficiency versus current density for example 5 of the present invention and comparative example 1;
FIG. 3 is a Photoluminescence (PL) spectrum of a compound prepared according to example 5 of the present invention in THF/water mixtures of different water contents.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
At room temperature, the compound represented by the formula (V) (2.69g, 10mmol) was added to a 100ml single-neck reaction flask, an appropriate amount of THF was added until the compound represented by the formula (V) was completely dissolved (about 80ml), liquid bromine (2ml, 40mmol) was dissolved in 3ml of THF solution, and the solution was added dropwise to the reaction system and was reacted for 8 hours with exclusion of light. Adding water to stop the reaction, extracting with DCM, washing with deionized water for several times, collecting organic solution, and concentrating. The crude product was isolated and purified by column chromatography to give the compound of formula (IV) (2.089g, 60% yield) according to the chemical reaction equation:
Figure BDA0003085969760000041
example 2
4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane (4.92g, 15mmol), a compound represented by the formula (IV) (3.48g, 10mmol) and a catalyst Pd (PPh)3)4(0.62g, 0.5mmol) was mixed in toluene (80 mL). Will K2CO3Aqueous solution (2.03g, 15mmol) was slowly added to the reaction mixture and after 30min of nitrogen gas was bubbled through, the reaction mixture was heated to 85 ℃ under nitrogen at reflux for 12h (reaction progress was monitored by TLC). After completion of the reaction, it was diluted with ethyl acetate (150 mL). The organic layer was washed with brine solution, water and anhydrous Na2SO4Drying, filtration and removal of the solvent in vacuo gave the product of the compound of formula (III) (3.18g, 68% yield) according to the chemical reaction equation:
Figure BDA0003085969760000051
example 3
A500 ml single-necked flask was charged with the compound represented by the formula (III) (11.7g, 25mmol), glacial acetic acid (25ml) and concentrated sulfuric acid (75ml) at 0 to 5 ℃ and stirred with exclusion of light. N-bromosuccinimide (NBS) (13.9g, 80mmol) was then added in three portions and allowed to warm to room temperature gradually, allowing the reaction to proceed overnight. Diluting the reaction mixture with a large amount of water, separating the solid, and then reusing NaHCO3The aqueous solution was washed with methanol several times, dried and then purified with a hot chlorobenzene solvent to obtain a compound represented by the formula (II) (13.76g, yield 75%) having the chemical reaction equation:
Figure BDA0003085969760000052
example 5
Under the condition of argon atmosphere and room temperature, Pd (OAc)2(0.14g, 0.63mmol), sodium carbonate (2.29g, 15mmol), triphenylphosphine (0.396g, 1.5mmol), a compound represented by the formula (II) (0.82g, 1.5mmol), dibenzoquinoxaline-2, 3-dicarbonitrile (0.7g, 2.5mmol) and ethylene glycol dimethyl ether (25ml) were charged in a 50ml two-necked flask, heated to 85 ℃ under nitrogen atmosphere, and reacted for 24 hours. Column chromatography (eluting with petroleum ether and dichloromethane 1: 2), and recrystallizing to obtain compound of formula (I) (0.91g, 81%) with the chemical reaction equation
Figure BDA0003085969760000061
Example 6
Firstly, processing ITO: repeatedly scrubbing the ITO surface with a glass cleaning solution, then sequentially carrying out ultrasonic treatment on the ITO surface with deionized water, ethanol, acetone and ethanol, and then carrying out drying treatment in a drying oven at 120 ℃ for 90 minutes. The ITO surface was then treated with UV-ozone for 5 minutes, and the cleaned glass was treated at a temperature of about 1X 10-6the pressure of the torr is transferred to the vacuum deposition system. The organic layer is thermally evaporated to
Figure BDA0003085969760000064
Are sequentially coated on the ITO substrate. By passing through
Figure BDA0003085969760000065
The thermal deposition of LiF is carried out at a rate to complete the cathode, and then at
Figure BDA0003085969760000066
The rate of deposition of metallic Al. The device structure is ITO/PEDOT, PSS (40nm)/TAPC (20nm)/EML (20nm)/TPBi (40nm)/LiF (1.5nm)/Al (100nm), wherein the PEDOT is PSS which is a hole injection layer material; TAPC is a hole transport layer; the compounds prepared in the examples of the invention asThe light-emitting layer (EML), TPBi as the Electron Transport Layer (ETL).
Comparative example 1
The comparative example differs from example 5 in that: replacement of Dibenzoquinoxaline-2, 3-dicarbonitrile with
Figure BDA0003085969760000062
Finally obtaining
Figure BDA0003085969760000063
(0.85g, yield 81%).
FIG. 1 is a PL photoluminescence spectrum of example 5 of the present invention and comparative example 1, wherein the Photoluminescence (PL) spectra were measured on a horiba Fluoromax-4 spectrometer. As is clear from FIG. 1, the compound produced in example 5 of the present invention had an emission wavelength of 652nm and was in the red region. The compound prepared in the comparative example 1 has an emission wavelength of 592nm and is orange red, and the compound in the example 5 has an obvious red shift compared with the compound in the comparative example 1, which shows that nitrile is introduced into dibenzoquinoxaline to be used as an acceptor, and the nitrile and the compound shown in the formula (II) form an A-D-A effect, so that the intramolecular charge transfer effect is improved, and an ICT phenomenon occurs to cause a spectrum red shift.
Fig. 2 is a graph of external quantum efficiency versus current density according to example 5 and comparative example 1, where the External Quantum Efficiency (EQE) is obtained by estimating the luminance, current density and light emission spectrum under the assumption of lambertian distribution, and it can be seen from fig. 2 that the example of the present invention forms an effective a-D-a effect, so that the carrier transport efficiency is enhanced, thereby effectively increasing the external quantum efficiency to more than 10%, and having a typical delayed fluorescence effect. The comparative example 1 is a common fluorescent compound, the external quantum efficiency of which is only about 1%, and the decrease of the example 5 is more gradual along with the increase of the current density, which shows that the compound prepared by the example of the present invention has higher charge transfer efficiency and can realize continuous and stable luminescence in the electroluminescent device, wherein table 1 shows specific electroluminescent performance data of the example 5 and the comparative example 1 of the present invention.
TABLE 1 data on the electroluminescent properties of the compounds prepared in inventive example 5 and comparative example 1
Examples PL S1(eV) T1(eV)) △EST Von L(cd/m2) EQE(％)
Example 5 652 2.94 2.82 0.12 2.2 12097 11.2％
Comparative example 1 592 2.98 2.46 0.52 3.4 6543 1.3％
As can be seen from Table 1, the compound of example 5 of the present invention has lower starting voltage, higher brightness, chromatographic purity and external quantum efficiency, and Δ E of example 5, compared to comparative example 1STLess than 0.2, and much more than 0.2 in comparative example 1, indicating that the compound of the present invention shows a significant TADF effect after introducing the acceptor with a stronger electron-withdrawing effect.
FIG. 3 is a Photoluminescence (PL) spectrum of a THF/water mixture with different water contents of the compound prepared in example 5 of the present invention, and it can be seen from the graph that the luminous intensity rapidly increases with the increase of the water content of the compound, which is attributable to the fact that in a mixed solution with a low water content, the compound is in a monomolecular state, and the active intramolecular rotational motion effectively dissipates the energy of the excited state as a nonradiative transition channel, so that the light emission is weak. It can be seen that the compounds prepared according to the invention have typical AIE properties.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (3)

1. A multifunctional delayed fluorescent material is characterized in that the structure is shown as formula (I):
Figure FDA0003085969750000011
2. a preparation method of a multifunctional delayed fluorescent material is characterized by comprising the steps of reacting a compound shown as a formula (II) with dibenzoquinoxaline-2, 3-dicarbonitrile to prepare a compound shown as a formula (I);
Figure FDA0003085969750000012
3. the method for preparing a multifunctional delayed fluorescence material according to claim 2, wherein the compound represented by formula (II) is prepared by the following steps:
step 1: reacting a compound shown in a formula (V) with liquid bromine to obtain a compound shown in a formula (IV);
Figure FDA0003085969750000013
Figure FDA0003085969750000021
step 2: reacting the compound shown in the formula (IV) with 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane to obtain a compound shown in a formula (III);
Figure FDA0003085969750000022
and step 3: reacting the compound shown in the formula (III) with NBS to obtain the compound shown in the formula (II).
CN202110580597.1A 2021-05-26 2021-05-26 Multifunctional delayed fluorescent material and preparation method thereof Withdrawn CN113321660A (en)

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Application publication date: 20210831