CN113234096A - Red light thermal activation delayed fluorescence material and preparation method thereof - Google Patents

Red light thermal activation delayed fluorescence material and preparation method thereof Download PDF

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CN113234096A
CN113234096A CN202110524487.3A CN202110524487A CN113234096A CN 113234096 A CN113234096 A CN 113234096A CN 202110524487 A CN202110524487 A CN 202110524487A CN 113234096 A CN113234096 A CN 113234096A
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方一文
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Nanchang Wanji Technology Co ltd
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Abstract

The invention belongs to the technical field of photoelectric display devices, and particularly relates to a red light thermal activation delayed fluorescent material and a preparation method thereof. The invention provides a red light thermal activation delayed fluorescent material, which has a structural formula shown as a formula (I). The invention also provides a preparation method of the red-light thermally-activated delayed fluorescent material, which comprises the steps of carrying out substitution reaction on (4-bromophenyl) (phenyl) (4- (pyridine-1-yl) phenyl) phosphine oxide and a compound shown as a formula (II) to prepare a compound shown as a formula (I); the invention provides a red-light thermally-activated delayed fluorescent material and a preparation method thereof, and solves the technical problems that the existing red TADF material is difficult to synthesize and the device efficiency is low.

Description

Red light thermal activation delayed fluorescence material and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric display devices, in particular to a red light thermal activation 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 electroluminescent tricolor material, the molecular synthesis of the material is difficult due to the red TADF. Therefore, the number of red molecular species is relatively small, and the device efficiency is not high.
Disclosure of Invention
The invention provides a red-light thermally-activated delayed fluorescent material and a preparation method thereof, and solves the technical problems that the existing red TADF material is difficult to synthesize and the device efficiency is low.
The invention provides a red light thermal activation delayed fluorescent material, which has a structural formula shown as a formula (I):
Figure BDA0003065301940000011
the invention also provides a preparation method of the red-light thermally-activated delayed fluorescence material, which comprises the step of carrying out coupling reaction on (4-bromophenyl) (phenyl) (4- (pyridine-1-yl) phenyl) phosphine oxide and 4, 9-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) naphthalene [2,3-c ] [1,2,5] thiadiazole to prepare the compound shown in the formula (I).
Preferably, the time of the substitution reaction is 8 to 20 hours.
The invention has the following beneficial effects:
the emission wavelength of the TADF material prepared by the embodiment of the invention is between 600nm and 700nm, the TADF material is red light emission, and the emission spectrum has obvious red shift along with the increase of the reaction time and can be attributed to ICT effect in a molecular structure. The brightness of the prepared compound is greatly improved along with the increase of the reaction time in the embodiment of the invention, and is from 4314cd/m2Increased to 8471cd/m2The external quantum efficiency can reach 23.4% at most.
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FIG. 1 is a nuclear magnetic hydrogen spectrum of a compound prepared in an example of the present invention;
FIG. 2 is a PL spectrum for examples 6-9 of the present invention.
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
Pyrene (2.02g, 10mmol) was dissolved in 50ml of hydrogen peroxide, and hydrogen bromide (1.21g, 15mmol), a mixed solution of ether and methanol (volume ratio ═ 1:2) was added to the above solution, stirred at 0 ℃ for 8h, and the resulting product was recrystallized in ethanol to give the product 1-bromopyrene (2.38g, yield 85%) whose chemical reaction equation was:
Figure BDA0003065301940000031
example 2
1-bromopyrene (2.81g, 10mmol), 2- (dimethyl-13-oxoalkyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane (3.46g,20mmol), 100ml of anhydrous tetrahydrofuran and butyllithium (40mmol) were added to a 250ml three-necked flask, and after introducing argon gas for 10min, the temperature was lowered to-78 ℃ to carry out a reaction for 28 hours, and after completion of the reaction, extraction purification treatment was carried out to obtain 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane (2.33g, yield 71%) as a product, the chemical reaction equation of which was:
Figure BDA0003065301940000032
example 3
To a 250mL dry single neck flask were added triphenylphosphine oxide (2.78g, 10mmol) and CCl4(20mL) was slowly added dropwise to the solution in CCl at room temperature4After dropwise addition of (10mL) liquid bromine (1.55mL, 30mmol), the mixture was refluxed for 8h while being heated, and after TLC monitoring reaction, the mixture was cooled and evaporated to dryness to obtain a pale yellow crude product. The crude product was dissolved in 30ml of THF and Et dissolved in 10ml of THF was added dropwise under ice-bath3N (50mL, 9.1mmol), after the addition was complete, the ice bath was removed and the mixture was stirred at room temperature for 4 h. After the reaction is finished, evaporating the solvent to dryness, adding ethyl acetate for extraction (30mL), combining organic phases, adding a saturated sodium chloride solution for backwashing, drying the mixture by anhydrous magnesium sulfate, carrying out rotary evaporation concentration, and carrying out column chromatography (V petroleum ether: V dichloromethane is 2: 1) to obtain a product, namely bis (4-bromophenyl) (phenyl) phosphine oxide (3.53g, the yield is 81%), wherein the chemical reaction equation is as follows:
Figure BDA0003065301940000041
example 4
4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane (3.28g, 10mmol) and potassium hydroxide (1.68g,30mmol) were dissolved in 150mL of dimethyl sulfoxide and heated to 75 ℃ under nitrogen at which time bis (4-bromophenyl) (phenyl) phosphine oxide (4.36g,10mmol) was slowly added and reacted for 12 h. The reaction was stopped and cooled to room temperature, and the reaction solution was poured into water and extracted with dichloromethane. Purification by column chromatography using 300-400 mesh silica gel as the stationary phase and petroleum ether/dichloromethane (1:2) as the eluent gave (4-bromophenyl) (phenyl) (4- (pyridin-1-yl) phenyl) phosphine oxide (4.12g, 74% yield) according to the equation:
Figure BDA0003065301940000042
example 5
The reactant 4, 9-dibromonaphtho [2,3-c ] [1,2,5] thiadiazole (4.13g,12mmol) was dissolved in 150ml tetrahydrofuran solvent which had been dehydrated in advance, and the mixture was placed in a low temperature reactor to be maintained at-78 ℃ and degassed three times, followed by nitrogen protection. After the system was stabilized, n-butyllithium (2.4M,5.3mL) was added dropwise to the above reaction system using a syringe, and stirred for three hours. 2-Isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborolan (4.66g,25mmol) was added dropwise to the reaction system. The reaction mixture turned a color of earthy yellow. After four hours of reaction, it was allowed to stir at room temperature for two days. The reaction mixture was extracted with water and a dichloromethane solvent, and the organic phase was dried over anhydrous sodium sulfate. The organic phase was concentrated by vacuum distillation. Separating by silica gel column chromatography, wherein the developing solvent is a mixed solvent of dichloromethane and petroleum ether (volume ratio is 1: 3). 4, 9-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) naphthalene [2,3-c ] [1,2,5] thiadiazole (2.376g, yield 45.2%) is obtained according to the following chemical reaction equation:
Figure BDA0003065301940000051
example 6
Under nitrogen atmosphere at-78 deg.CNext, to a suspension of (4-bromophenyl) (phenyl) (4- (pyridin-1-yl) phenyl) phosphine oxide (5.57g, 10mmol) in anhydrous THF (120mL) was added dropwise n-butyllithium (6.4mL, 12.8mmol, 2.0M in cyclohexane). Stirring was continued for 3h, then 4, 9-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthothiadiazole (6.255g, 12mmol) was added, the mixed solution was warmed to 80 ℃ and after stirring for 8h, the reaction was monitored by TLC, the resulting organic compound was extracted with dichloromethane, the obtained residue was dissolved in dichloromethane (50ml), after stirring at room temperature for 6h, the organic phase was washed with anhydrous Na2SO4And (4) extracting. The crude product obtained was subjected to silica gel column chromatography (petroleum ether: dichloromethane (1: 3) as eluent) to obtain compound 1(7.54g, yield 67%) whose chemical reaction equation is:
Figure BDA0003065301940000052
example 7
The difference between this example and example 6 is: the reaction time of example 6 was 8h, and the reaction time of example 7 was 12h, to finally obtain compound 2(5.97g, yield 71%).
Example 8
The difference between this example and example 6 is: the reaction time of example 6 was 8h, and that of example 8 was 16h, to finally obtain compound 3(5.94g, yield 70%).
Example 9
The difference between this example and example 6 is: the reaction time of example 6 was 8h and the reaction time of example 9 was 20h, to finally obtain compound 4(5.99g, yield 70%).
In conclusion, the PL spectrum test is carried out by adopting a Fluoromax-4 fluorescence spectrometer of HORIBA company; testing the fluorescence quantum yield by a HAMAMATSU C11347 fluorescence quantum tester; TADF material was tested for brightness, ignition voltage, etc. using a Keithley236 instrument and calibrated with a silicon photodiode. Transient lifetime testing and delayed lifetime were determined using an Edinburgh Instruments FLS 980 spectrometer. Outside the nitrogen glove box, the color coordinates CIE were determined with a Photo Research PR705 type optical analyzer after the device was encapsulated.
The preparation process of the device comprises the following steps:
the preparation of the organic electroluminescent diode needs the following processes:
1) and putting the film developing frame with the ITO glass substrate in acetone, isopropanol, a washing solution and deionized water, and ultrasonically treating the possibly residual stains, such as photoresist and the like, on the surface of the ITO glass substrate by using an ultrasonic device and improving interface contact. Then drying in a vacuum oven;
2) placing the ITO in an oxygen Plasma etching instrument, continuously bombarding the ITO for 30 minutes by using O2 Plasma, and completely removing possible residual organic matters on the surface of the ITO glass substrate;
3) HAT-CN was spin-coated on the ITO to a thickness of 10nm, and functions to reduce the influence of leakage current while increasing hole injection. Then drying the mixture in a vacuum oven for 12 hours at a temperature of 75 ℃;
4) in a glove box under nitrogen atmosphere, α -NPD was spin-coated on the HAT-CN layer to a thickness of about 40nm and heated at 100 ℃ for 30 minutes to remove the residual solvent.
5) And a layer of luminous organic matter film is spin-coated on the alpha-NPD layer, and the thickness is 80 nm. Heating and annealing for 20 minutes at the temperature of 80 ℃ on a heating table to remove residual solvent and improve the appearance of the luminescent layer film;
6) in the vacuum evaporation chamber, a layer of lithium fluoride (LiF) which is helpful for electron injection is firstly evaporated on the luminescent layer, and the thickness is 1.5 nm. Then, a layer of aluminum (Al) cathode is evaporated, and the thickness is 150 nm.
The effective area of the device is 0.18cm2. The thickness of the organic layer was measured by a quartz crystal monitoring thickness gauge. The device is prepared by polar curing and encapsulating in ultraviolet light with epoxy resin and thin-layer glass.
In summary, FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound prepared in the example of the present invention. FIG. 2 shows PL spectra of examples 6-9 of the present invention, and it can be seen from FIG. 1 that TADF materials prepared according to the examples of the present invention have red light emission with an emission wavelength of 600nm-700nm, and the emission spectra are significantly red-shifted with increasing reaction time, and can be attributed to ICT effect in the molecular structure. In particular, the photophysical data for the novel TADF materials obtained in examples 6-9 of the present invention are shown in Table 1,
TABLE 1 photophysical data for TADF materials obtained according to examples 6-9 of the present invention
Figure BDA0003065301940000071
As can be seen from table 1, the color coordinates of the TADF materials prepared in examples 6 to 9 of the present invention all show red light emission, the fluorescence quantum yields of the TADF materials prepared in examples 6 to 9 of the present invention are all above 80%, and the transient decay lifetime τ p (ns) of the present invention is small, indicating that the roll-off of the electroluminescence efficiency of the present invention is small.
The invention uses ITO (120nm)/HAT-CN (10 nm)/alpha-NPD (40nm)/emitter (80nm)/LiF (1.5nm)/Al (150nm) as a device, and TADF materials prepared in examples 6-9 as a light-emitting layer, wherein HAT-CN and alpha-NPD respectively refer to 1,4,5,8,9, 12-hexaazatriphenylene hexacyano-nitrile and 4,4' -bis (N- (naphthalene-1-yl) -N-phenylamino) biphenyl, and specific electroluminescent performance data are shown in Table 2.
Table 2 electroluminescent property data for examples 6-9
Examples Von L(cd/m2) EQE(％)
Example 6 6.4 4314 15.3
Example 7 6.2 5423 17.4
Example 8 5.8 6978 21.6
Example 9 5.6 8471 23.4
As can be seen from Table 2, the luminance of the compound obtained in the example of the present invention is greatly improved from 4314cd/m with the increase of the reaction time2Increased to 8471cd/m2The external quantum efficiency can reach 23.4% at most, and the external quantum efficiency of the TADF material prepared by the embodiment of the invention is more than 15%, which shows that reverse system jump of T1-S1 exists in the molecular structure, and the current efficiency is remarkably improved along with the rise of voltage in the embodiment of the invention, which shows that the TADF material prepared by the embodiment of the invention has smaller resistance and better carrier transmission efficiency.
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 red-light thermally-activated delayed fluorescent material is characterized in that the structural formula is shown as the formula (I):
Figure FDA0003065301930000011
2. a preparation method of a red-light thermally-activated delayed fluorescence material is characterized by comprising the step of carrying out coupling reaction on (4-bromophenyl) (phenyl) (4- (pyridin-1-yl) phenyl) phosphine oxide and 4, 9-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) naphthalene [2,3-c ] [1,2,5] thiadiazole to prepare a compound shown in a formula (I).
3. The method for preparing a red-light thermally-activated delayed fluorescence material according to claim 2, wherein the time of the substitution reaction is 8-20 h.
CN202110524487.3A 2021-05-13 2021-05-13 Red light thermal activation delayed fluorescence material and preparation method thereof Withdrawn CN113234096A (en)

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Application publication date: 20210810