CN113527322A - Preparation method of chiral thermal activation delayed fluorescent material - Google Patents

Preparation method of chiral thermal activation delayed fluorescent material Download PDF

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CN113527322A
CN113527322A CN202110827376.XA CN202110827376A CN113527322A CN 113527322 A CN113527322 A CN 113527322A CN 202110827376 A CN202110827376 A CN 202110827376A CN 113527322 A CN113527322 A CN 113527322A
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唐建新
谢凤鸣
李艳青
周经雄
曾馨逸
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Abstract

The invention relates to a preparation method of a chiral thermal activation delayed fluorescent material, which takes 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine) and 5,5',6,6',7,7',8,8' -octahydrobinaphthol as raw materials, and the chiral thermal activation delayed fluorescent material R1 and S1 are prepared by reaction; or 10,10' - ((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) and 5,5',6,6',7,7',8,8' -octahydrobinaphthol are used as raw materials to prepare the chiral thermal activation delayed fluorescence materials R2 and S2 through reaction.

Description

Preparation method of chiral thermal activation delayed fluorescent material
The invention relates to a chiral thermal activation delayed fluorescence material and a preparation method thereof, and a divisional application of the invention with the application number of CN2020109374617 and the application date of 2020, 9, 8, belonging to the technical part of the preparation method.
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a preparation method of a chiral thermal activation delayed fluorescent material which is applicable to industrialization and has good performance.
Background
Organic Light Emitting Diodes (OLEDs) are attracting much attention due to their great applications in light sources, flexible flat panel displays. The first generation of light emitting devices OLEDs based on conventional fluorescent materials showed Internal Quantum Efficiencies (IQE) as high as 25% and External Quantum Efficiencies (EQE) of 5-7.5%, since the emissive material can only obtain singlet excitons. The second generation phosphorescent material containing noble metal atoms can effectively utilize singlet excitons and triplet excitons to carry out spin-orbit coupling, and the IQE can reach 100%; however, in view of their rarity and high cost, iridium (Ir) and platinum (Pt) have been largely limited in their applications in the field of organic light emitting materials. The third generation light emitting material, a Thermally Activated Delayed Fluorescence (TADF) material, which is emerging in recent years, does not contain metal, and the TADF material can pass triplet excitons from the lowest triplet excited state (T)1) By intersystem crossing to the singlet excited state (S)1) In addition, the conversion into photons can also lead the IQE to reach 100 percent, and the material is a phosphorescent luminescent material with extremely wide potential and prospectAnd thus has attracted considerable attention in the field of organic electroluminescence in the last few years.
Circular Polarization Light (CPL) is receiving great attention for its potential applications in 3D imaging, information storage, quantum computing, etc. Meanwhile, TADF organic light emitting materials theoretically achieve 100% internal quantum efficiency without noble metals, and are a hot point of research. At present, CPL-TADF is realized mainly by directly grafting a chiral small molecular fragment onto a TADF molecular skeleton, however, further expansion of the molecular fragment is limited due to complex molecular design and synthesis, so that the development of a novel, simple and efficient chiral TADF material becomes a current research hotspot.
Disclosure of Invention
The invention discloses a chiral thermal activation delayed fluorescence material and a preparation method thereof, wherein the chemical name of the chiral thermal activation delayed fluorescence material is R/S-18, 21-di (10H-phenoxazin-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ] dibenzo]Dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4]Dioxin [2,3-i ]]Phenazine or R/S-16, 17-bis (4- (10H-phenoxazin-10-yl) phenyl) -3,4,5,6,7,8,9, 10-octahydro-naphtho [2', 1': 5,6, 1', 2': 7,8] [1,4]Dioxane [2,3-g ]]Quinoxaline is used for solving the problems that the chiral delayed fluorescence luminescent material is difficult to synthesize and prepare, the material types are few, and the efficiency of the circular polarization delayed fluorescence device is low; meanwhile, the problems that the existing orange red light/red light TADF material has multiple synthesis and preparation steps, expensive raw materials, complex synthesis and purification process, low yield and difficult large-scale mass production are solved; particularly, the CP-OLED prepared by the chiral thermal activation delayed fluorescence material doped with the luminescent layer realizes that the EQE of the CP-OLED exceeds 20 percent, and the asymmetric factor g is more than 10-3The object of (1).
The invention adopts the following technical scheme:
a chiral thermal activation delayed fluorescence material has the following chemical structural formula:
Figure 992123DEST_PATH_IMAGE001
。
on one hand:
the preparation method of the chiral orange red photothermal activation delayed fluorescence material comprises the following steps: the chiral orange red photo-thermal activation delayed fluorescent materials R1 and S1 are prepared by taking 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine) and 5,5',6,6',7,7',8,8' -octahydrobinaphthol as raw materials through reaction; the reaction can be referred to as follows:
Figure 174842DEST_PATH_IMAGE002
further, the mol ratio of 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine) to 5,5',6,6',7,7',8,8' -octahydrobinaphthol is 1: 0.8-1.1; the reaction is carried out in the presence of alkali and under the protection of nitrogen; the reaction temperature is 40-100 ℃, and the reaction time is 12-24 h. After the reaction is finished, extracting reaction liquid, then combining organic phases, and performing suction filtration to obtain the chiral orange red photothermal activation delayed fluorescence material; preferably, the extraction solvent may be any one of dichloromethane, chloroform, ethyl acetate, glacial acetic acid or some combination of these solvents.
In the invention, 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine and 10H-phenoxazine are used as raw materials to prepare 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine) through reaction; preferably, the molar ratio of the 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine to the 10H-phenoxazine is 1: 2.2-2.6; the reaction is carried out in the presence of a palladium catalyst; the reaction temperature is 90-130 ℃, and the reaction time is 20-28 h; the reaction can be referred to as follows:
Figure 656377DEST_PATH_IMAGE003
further, the reaction is carried out in the presence of a palladium catalyst, sodium tert-butoxide and a phosphine ligand; preferably, the molar ratio of the sodium tert-butoxide to the 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine to the palladium catalyst is 3-6: 1: 0.01-0.1, and the molar ratio of the palladium catalyst to the phosphine ligand is 1: 1; the palladium catalyst is tri (dibenzylidene acetone) dipalladium (0), and the phosphine ligand is tri-tert-butylphosphine tetrafluoroborate.
The chiral orange red photothermal activation delayed fluorescence material is R/S-18, 21-di (10H-phenoxazin-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ]]Dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4]Dioxin [2,3-i ]]A phenazine of the formula: c64H44N4O4The chemical structural formula is as follows:
Figure 989269DEST_PATH_IMAGE004
the preparation method of the chiral orange red photothermal activation delayed fluorescence material can comprise the following steps:
(1) 4, 5-difluorobenzene-1, 2-diamine and 3, 6-dibromo-9, 10-phenanthrenequinone react to obtain 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine;
(2) carrying out C-N coupling reaction on the 3, 6-dibromo-11, 12-difluorodibenzo [ a, C ] phenazine obtained in the step (1) and 10H-phenoxazine to obtain 10,10' - (11, 12-difluorodibenzo [ a, C ] phenazine-3, 6-diyl) bis (10H-phenoxazine);
(3) reacting the 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine) obtained in the step (2) with R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol to obtain a chiral thermally activated delayed fluorescence material R/S-18, 21-bis (10H-phenoxazine-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ] dinaphtho [2',1 ': 5,6, 1', 2': 7,8] [1,4] Dioxin [2,3-i ] phenazine.
Further, in the step (1), the molar ratio of 4, 5-difluorobenzene-1, 2-diamine to 3, 6-dibromo-9, 10-phenanthrenequinone is 1.1-1.3: 1; the reaction is carried out under the protection of nitrogen, absolute ethyl alcohol is used as a solvent, the reaction temperature is 70-90 ℃, and the reaction time is 1.0-4.0 h; after the reaction is finished, filtering the reaction liquid, and recrystallizing the obtained filter cake to obtain a light yellow solid 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine; further, the solvent for recrystallization is any one of absolute ethyl alcohol, dichloromethane, trichloromethane and acetic acid or a certain combination of the solvents; the reaction in step (1) can be referred to as follows:
Figure 741325DEST_PATH_IMAGE005
on the other hand:
the preparation method of the chiral yellow light thermal activation delayed fluorescent material comprises the following steps: the chiral yellow thermally-activated delayed fluorescent materials R2 and S2 are prepared by taking 10,10' - (((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) and 5,5',6,6',7,7',8,8' -octahydrobinaphthol as raw materials through reaction, wherein the reaction can be referred to as follows:
Figure 704733DEST_PATH_IMAGE006
further, the molar ratio of 10,10' - (((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) to 5,5',6,6',7,7',8,8' -octahydrobinaphthol is 1: 0.8-1.1, the reaction is carried out in the presence of alkali and under the protection of nitrogen, the reaction temperature is 40-100 ℃, the reaction time is 12-24H, after the reaction is finished, the reaction liquid is extracted, organic phases are combined, and then suction filtration is carried out to obtain the chiral yellow light thermal activation delayed fluorescent material, preferably, the extraction solvent can be any one of dichloromethane, trichloromethane, ethyl acetate and glacial acetic acid or a certain combination of the solvents.
According to the invention, 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline and 10H-phenoxazine are used as raw materials to prepare 10,10' - (((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) through reaction, preferably, the molar ratio of the 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline to the 10H-phenoxazine is 1: 2.2-2.6, the reaction is carried out in the presence of a palladium catalyst, the reaction temperature is 90-130 ℃, the reaction time is 20-28H, and the following reactions can be referred to:
Figure 676493DEST_PATH_IMAGE007
further, the reaction is carried out in the presence of a palladium catalyst, sodium tert-butoxide and a phosphine ligand; preferably, the molar ratio of the sodium tert-butoxide to the 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline to the palladium catalyst is 3-6: 1: 0.01-0.1, and the molar ratio of the palladium catalyst to the phosphine ligand is 1: 1; the palladium catalyst is tri (dibenzylidene acetone) dipalladium (0), and the phosphine ligand is tri-tert-butylphosphine tetrafluoroborate.
The chiral yellow-light thermally-activated delayed fluorescent material is R/S-16, 17-bis (4- (10H-phenoxazin-10-yl) phenyl) -3,4,5,6,7,8,9, 10-octahydro-naphtho [2', 1': 5,6, 1', 2': 7,8] [1,4]Dioxane [2,3-g ]]Quinoxaline of the formula: c64H46N4O4The chemical structural formula is as follows:
Figure 813076DEST_PATH_IMAGE008
the preparation method of the chiral yellow light thermal activation delayed fluorescence material can comprise the following steps:
(1) reacting 4, 5-difluorobenzene-1, 2-diamine and 1, 2-bis (4-bromophenyl) ethane-1, 2-diketone to obtain 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline;
(2) carrying out C-N coupling reaction on the 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline obtained in the step (1) and 10H-phenoxazine to obtain 10,10' - ((((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine);
(3) reacting the 10,10' - (((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) obtained in the step (2) with R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol to obtain the chiral thermally activated delayed fluorescence material R/S-16, 17-bis (4- (10H-phenoxazin-10-yl) phenyl) -3,4,5,6,7,8,9, 10-octahydro-naphtho [2',1 ': 5,6; 1' ',2' ': 7,8] [1,4] dioxan [2,3-g ] quinoxaline.
Further, in the step (1), the molar ratio of 4, 5-difluorobenzene-1, 2-diamine to 1, 2-bis (4-bromophenyl) ethane-1, 2-dione is 1.1-1.3: 1; the reaction is carried out under the protection of nitrogen, absolute ethyl alcohol is used as a solvent, the reaction temperature is 70-90 ℃, and the reaction time is 1.0-4.0 h; after the reaction is finished, filtering the reaction liquid, and recrystallizing the obtained filter cake to obtain a light yellow solid 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline; further, the solvent for recrystallization is any one of absolute ethyl alcohol, dichloromethane, trichloromethane and acetic acid or a certain combination of the solvents; the reaction in step (1) can be referred to as follows:
Figure 747534DEST_PATH_IMAGE009
the invention discloses application of the chiral thermal activation delayed fluorescence material in preparation of an organic electroluminescent device. The light emitting layer of the organic electroluminescent device comprises the chiral thermal activation delayed fluorescence material, and the chiral thermal activation delayed fluorescence material is used as a guest material and doped with a host material to be used as the light emitting layer; furthermore, the doping concentration of the chiral thermal activation delayed fluorescence material is 2-20 wt%.
The organic electroluminescent device based on the chiral thermal activation delayed fluorescence material disclosed by the invention is characterized in that Indium Tin Oxide (ITO) is used as an anode, and the ratio of double pyrazino [2, 3-f: 2', 3' -H ] quinoxaline-2, 3,6,7,10, 11-Hexanenitrile (HATCN) as Hole Injection Layer (HIL), 4' - (cyclohexane-1, 1-diyl) bis (N, N-di-p-Tolylaniline) (TAPC) as Hole Transport Layer (HTL), tris (4- (9H-carbazol-9-yl) phenyl) amine (TCTA) as electron/Exciton Blocking Layer (EBL), 4' -bis (9H-carbazol-9-yl) -1,1' -biphenyl (CBP) host material doped with the chiral thermally activated delayed fluorescent material, together as light-emitting layer (EML), 4, 6-bis (3, 5-bis (pyridin-3-yl) phenyl) -2-methylpyrimidine (B3 MPM) as Electron Transport Layer (ETL), 8-hydroxyquinoline-lithium (Liq) was used as the Electron Injection Layer (EIL), and aluminum (Al) was used as the cathode; further, the specifications of each layer of the organic electroluminescent device are as follows: ITO/HATCN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/CBP: R/S-TADF material (X wt%) (20 nm)/B3PYMPM (50 nm)/Liq (2 nm)/Al (100 nm).
The invention provides a novel chiral thermal activation delayed fluorescent materialA synthetic preparation method of the material; and an OLED based on the chiral thermally activated delayed fluorescence material, wherein the EQE of the OLED is more than 20%, and the asymmetry factor of the OLED is more than 10-3The target of (1); the method is used for solving the problems that the chiral delayed fluorescence luminescent material is difficult to synthesize and prepare, the material types are few, and the efficiency of the circular polarization delayed fluorescence device is low; meanwhile, the problems that the existing orange red light/red light TADF material has multiple synthesis and preparation steps, expensive raw materials, complex synthesis and purification process, low yield and difficult large-scale mass production are solved.
The preparation method of the organic electroluminescent device formed on the basis of the chiral orange red photothermal activation delayed fluorescence material and other raw materials are not particularly limited. The organic film formed by the invention has high surface smoothness, stable chemical and physical properties, high luminous efficiency and circular polarization light property, and the formed circular polarization organic electroluminescent device has good performance.
The invention has the following beneficial effects:
1. the invention provides a method for preparing R/S-18, 21-di (10H-benzene oxazine-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ] dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4] dioxin [2,3-i ] phenazine or R/S-16, 17-bis (4- (10H-phenoxazin-10-yl) phenyl) -3,4,5,6,7,8,9, 10-octahydro-naphtho [2', 1': 5,6, 1', 2': the 7,8] [1,4] dioxane [2,3-g ] quinoxaline thermal activation delayed fluorescence material has the characteristics of a rigid large plane distortion structure and obvious Internal Charge Transfer (ICT), and has the advantages of thermal activation delayed fluorescence property (TADF), Circular Polarization Luminescence (CPL), high fluorescence quantum yield (PLQY), good thermal stability and the like.
2. The CP-OLED device based on the chiral thermal activation delayed fluorescence material provided by the invention has the advantages of low driving voltage and good luminescence stability, the external quantum efficiency EQE of the prepared circular polarization device is respectively as high as 28.3 percent and 20.3 percent, and the unpaired factor g is respectively as high as 6 multiplied by 10-4And 2.4X 10-3。
3. The chiral thermal activation delayed fluorescence material provided by the invention has the advantages of few synthesis and preparation steps, easily available raw materials, simple synthesis and purification process, high yield and large-scale synthesis and preparation. The organic electroluminescent device based on the chiral unit has good application prospects in the fields of illumination, flat panel display, sensing, night vision, biological imaging and the like, the introduction of the chiral unit is that the material is not limited to the application, and the circular polarization luminescent device in the field also has potential application prospects in the aspects of 3D imaging, information storage, quantum computing and the like.
Drawings
FIG. 1 shows the nuclear magnetic hydrogen spectrum of the compound R-ODPPXZ prepared in example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of the compound R-ODPPXZ prepared in example 1.
FIG. 3 is a mass spectrum of R-ODPPXZ compound prepared in example 1.
FIG. 4 is an HPLC chromatogram of the compound R-ODPPXZ prepared in example 1.
FIG. 5 is an HPLC chromatogram of the compound S-ODPPXZ prepared in example 1.
FIG. 6 shows the nuclear magnetic hydrogen spectrum of the compound R-ODQPXZ prepared in example 2.
FIG. 7 shows the nuclear magnetic carbon spectrum of the compound R-ODQPXZ prepared in example 2.
FIG. 8 is a mass spectrum of the compound R-ODQPXZ prepared in example 2.
FIG. 9 shows an HPLC chromatogram of R-ODQPXZ compound prepared in example 2.
FIG. 10 shows an HPLC chromatogram of the compound S-ODQPXZ prepared in example 2.
FIG. 11 is a circular dichroism spectrum of the compound prepared in examples 1 and 2.
FIG. 12 shows circularly polarized spectra of the compounds prepared in examples 1 and 2 under thin film conditions.
Fig. 13 is a graph of device performance for application examples one and two.
Fig. 14 is a device efficiency graph of application example (one).
Fig. 15 is a graph of device efficiency of application example (two).
FIG. 16 is the nuclear magnetic hydrogen spectrum of compound R-OBPDMAC.
FIG. 17 is a nuclear magnetic carbon spectrum of compound R-OBPDMAC.
FIG. 18 is a mass spectrum of compound R-OBPDMAC.
Detailed Description
The raw materials involved in the invention are all conventional commercial products, and the specific operation method and the test method are conventional methods in the field; in particular, the specific preparation process of the organic electroluminescent device based on the chiral thermal activation delayed fluorescence material and the materials of each layer adopt the prior art, such as vacuum evaporation, the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, a deposition rate of the functional layer of 2A/s, a deposition rate of the host material of 1A/s, a deposition rate of the LiF layer of 0.1A/s, a deposition rate of Al of 8A/s. The invention creatively provides a novel chiral thermally activated delayed fluorescence material, and a doped host material is jointly used as a light emitting layer of an organic electroluminescent device.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the descriptions are intended to further illustrate the features and advantages of the invention and are not intended to limit the scope of the claims which follow
The invention provides a chiral thermal activation delayed fluorescence material R/S-18, 21-di (10H-benzoxazine-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ] dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4] Dioxin [2,3-i ] phenazine (R/S-ODPPXZ) and R/S-16, 17-bis (4- (10H-phenoxazin-10-yl) phenyl) -3,4,5,6,7,8,9, 10-octahydronaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4] dioxane [2,3-g ] quinoxaline (R/S-ODQPXZ).
The structural formula is as follows:
Figure 944161DEST_PATH_IMAGE010
example 1
The reaction formula is as follows:
Figure 636173DEST_PATH_IMAGE011
the reaction is as follows:
0.45 g (3.12 mmol) of 4, 5-difluorobenzene-1, 2-diamine and 1.12 g (3.06 mmol) of 3, 6-dibromo-9, 10-phenanthrenequinone are added into a 150 mL three-neck flask, 100 mL of absolute ethyl alcohol is added as a solvent, the mixture is stirred under the protection of nitrogen, the mixture reacts for 2 hours at the temperature of 80 ℃, then the reaction solution is filtered, and a filter cake is recrystallized by the absolute ethyl alcohol to obtain 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine as a light yellow solid, wherein the yield is 95%.
0.50 g (1.05 mmol) of 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine, 0.40 g (2.18 mmol) of 10H-phenoxazine, 0.41 g (4.27 mmol) of sodium tert-butoxide, 0.016 g (0.055 mmol) of tri-tert-butylphosphine tetrafluoroborate and 0.05 g (0.055 mmol) of tris (dibenzylideneacetone) dipalladium (0) are added into a 150 mL three-neck flask in sequence, 50 mL of toluene is added as a solvent, and the mixture is heated and reacted at 100 ℃ under the protection of nitrogen; after the reaction is finished, extracting with 100 mL of dichloromethane, combining organic phases, performing suction filtration, and separating and purifying the product by adopting a column chromatography (petroleum ether/dichloromethane, volume ratio is 1: 2) method to obtain a deep red solid 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine), wherein the yield is 80%.
0.50 g (0.74 mmol) of 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine), 0.22 g (0.75 mmol) of R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol and 0.35 g (2.53 mmol) of potassium carbonate are added into a 150 mL three-neck flask, and DMF (50 mL) is added as a solvent, and the mixture is stirred for reaction at 70 ℃ under the protection of nitrogen; after the reaction is finished, extracting with 100 mL of dichloromethane, combining organic phases and carrying out suction filtration; the product is separated and purified by adopting a column chromatography (petroleum ether/dichloromethane, volume ratio is 1: 2) method to obtain a final product R/S-18, 21-di (10H-benzoxazine-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ] dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4] Dioxin [2,3-i ] phenazine, at a yield of 70%.
The eluent for column chromatography is prepared by mixing one of organic solvents with small polarity such as petroleum ether, isopentane, n-pentane, hexane, cyclohexane and the like with another organic solvent with large polarity, such as dichloromethane, trichloromethane, ethyl acetate, ethanol and the like, and the volume ratio of the eluent is 1: 2 to 5.
The selection of R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol can lead to the corresponding chiral product. FIG. 1 shows the nuclear magnetic hydrogen spectrum of the compound R-ODPPXZ obtained above; FIG. 2 is a nuclear magnetic carbon spectrum of the compound R-ODPPXZ obtained above; FIG. 3 is a mass spectrum of the compound R-ODPPXZ obtained above; FIG. 4 is an HPLC chromatogram of the compound R-ODPPXZ obtained above; FIG. 5 shows an HPLC chromatogram of the compound S-ODPPXZ obtained above. The structure detection of the compound R-ODPPXZ is as follows:
1H NMR (400 MHz, CDCl3) δ 9.65 (d, J = 8.5 Hz, 2H), 8.50 (d, J = 1.8 Hz, 2H), 8.15 (s, 2H), 7.77 (dd, J = 8.5, 1.8 Hz, 2H), 7.16 (s, 4H), 6.75 (dd, J = 7.9, 1.5 Hz, 4H), 6.68 (td, J = 7.6, 1.4 Hz, 4H), 6.59 (td, J = 7.7, 1.6 Hz, 4H), 6.05 (dd, J = 7.9, 1.4 Hz, 4H), 2.92 – 2.75 (m, 6H), 2.53 (dt, J= 17.6, 6.0 Hz, 2H), 1.92 – 1.84 (m, 6H), 1.78 – 1.71 (m, 2H)；
13C NMR (101 MHz, CDCl3) δ 153.29, 150.97, 143.98, 141.12, 140.99, 140.61, 137.00, 135.53, 134.13, 133.73, 130.94, 130.35, 130.02, 129.46, 125.73, 123.33, 121.69, 119.72, 118.61, 115.65, 113.32, 29.39, 27.76, 22.80, 22.66；
MALDI-TOF MS (ESI, m/z) calcd for C64H44N4O4 [M+]: 932.34, Found: 932.701。
example 2
The reaction formula is as follows:
Figure 12666DEST_PATH_IMAGE012
the reaction is as follows:
0.45 g (3.12 mmol) of 4, 5-difluorobenzene-1, 2-diamine and 1.12 g (3.04 mmol) of 1, 2-bis (4-bromophenyl) ethane-1, 2-dione are added into a 150 mL three-neck flask, then 100 mL of absolute ethyl alcohol is added as a solvent, stirring is carried out under the protection of nitrogen, the reaction is carried out for 2 hours at 80 ℃, then the reaction solution is filtered, and a filter cake is recrystallized by the absolute ethyl alcohol to obtain a light yellow solid 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline, wherein the yield is 95%.
A150 mL three-neck flask was charged with 1.00 g (2.10 mmol) of 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline, 0.80 g (4.36 mmol) of 10H-phenoxazine, 1.00 g (10.4 mmol) of sodium tert-butoxide, 0.032 g (0.11 mmol) of tri-tert-butylphosphine tetrafluoroborate, 0.10 g (0.11 mmol) of tris (dibenzylideneacetone) dipalladium (0) in succession, 50 mL of toluene was added as a solvent, and the mixture was heated to react at 100 ℃ under nitrogen protection; after the reaction is finished, extracting with 100 mL of dichloromethane, combining organic phases, carrying out suction filtration, and separating and purifying the product by adopting a column chromatography (petroleum ether/dichloromethane, volume ratio is 1: 2) method to obtain orange solid 10,10' - ((((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) with the yield of 80%.
Adding 0.50 g (0.73 mmol) of 10,10' - (((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine), 0.21 g (0.71 mmol) of R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol and 0.25 g (1.81 mmol) of potassium carbonate into a 150 mL three-neck flask, adding DMF (50 mL) as a solvent, stirring at 70 ℃ for reaction under the protection of nitrogen, extracting with 100 mL of dichloromethane after the reaction is finished, combining organic phases, carrying out suction filtration, separating and purifying the product by adopting a column chromatography (petroleum ether/dichloromethane with the volume ratio of 1: 2) to obtain a final product R/S-16, 17-bis (4- (10H-phenoxazin-10-yl) phenyl) -3,4,5,6,7,8,9, 10-octahydro-dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4] dioxane [2,3-g ] quinoxaline in a yield of 70%.
The eluent for column chromatography is prepared by mixing one of organic solvents with small polarity such as petroleum ether, isopentane, n-pentane, hexane, cyclohexane and the like with another organic solvent with large polarity, such as dichloromethane, trichloromethane, ethyl acetate, ethanol and the like, and the volume ratio of the eluent is 1: 2 to 5.
The selection of R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol can lead to the corresponding chiral product. FIG. 6 shows the nuclear magnetic hydrogen spectrum of the compound R-ODQPXZ obtained above; FIG. 7 is a nuclear magnetic carbon spectrum of the compound R-ODQPXZ obtained above; FIG. 8 is a mass spectrum of the compound R-ODQPXZ obtained above; FIG. 9 is an HPLC chromatogram of the compound R-ODQPXZ obtained above; FIG. 10 shows an HPLC chromatogram of the compound S-ODQPXZ obtained above. The structure detection of the compound R-ODQPXZ is as follows:
1H NMR (400 MHz, CDCl3) δ 8.04 (s, 2H), 7.77 (d, J = 8.3 Hz, 4H), 7.40 (d, J = 8.3 Hz, 4H), 7.15 (d, J = 8.3 Hz, 2H), 7.09 (d, J = 8.2 Hz, 2H), 6.71 (dd, J = 7.8, 1.3 Hz, 4H), 6.64 (t, J = 7.0 Hz, 2H), 6.57-6.49 (m, 4H), 5.97 (d, J = 7.9 Hz, 4H), 2.92-2.74 (m, 7H), 2.51 (dt, J = 16.9, 5.7 Hz, 2H), 1.92-1.82 (m, 7H), 1.73 (dt, J = 13.3, 5.5 Hz, 2H).
13C NMR (101 MHz, CDCl3) δ 153.06, 151.86, 150.86, 143.90, 139.30, 139.06, 136.96, 135.52, 133.94, 132.59, 130.86, 130.07, 130.04, 123.41, 121.56, 120.00, 118.50, 115.55, 113.15, 29.37, 27.74, 22.78, 22.64.
MALDI-TOF MS (ESI, m/z) calcd for C64H46N4O4 [M+]: 934.35, Found: 935.660.
from the above results, it was found that the structures of the compounds R-ODPPXZ and R-ODQPXZ were correct.
The effect of the compound synthesized by the present invention as a guest material of a light-emitting layer in a device is illustrated by the following application examples.
Application examples
(I) preparation and Performance evaluation of organic electroluminescent device with 7wt% doping concentration R-ODPPXZ as light emitting layer
The manufacturing steps of the organic electroluminescent device with the light-emitting layer of R-ODPPXZ with the doping concentration of 7wt% are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 7wt% R-ODPPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device having light-emitting layer of R-ODPPXZ with doping concentration of 7wt%
Applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 1, table 2 and fig. 13.
(II) preparation and performance evaluation of organic electroluminescent device with 15wt% doping concentration R-ODQPXZ as light-emitting layer
The manufacturing steps of the organic electroluminescent device with the light-emitting layer as R-ODQPXZ with the doping concentration of 15wt% are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 15wt% R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device having light-emitting layer of R-ODQPXZ with doping concentration of 15wt%
Applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The light emitting properties of the organic electroluminescent device were measured under the condition that the applied direct current voltage was changed. Device performance is shown in table 1, table 2 and fig. 13.
Figure 739313DEST_PATH_IMAGE013
Figure 106840DEST_PATH_IMAGE014
FIG. 14 is a graph of device efficiency for application example (one); fig. 15 is a graph of device efficiency of application example (two).
Application examples
(III) preparation and performance evaluation of organic electroluminescent device with light-emitting layer of R-ODPPXZ with doping concentration of 3wt%
The manufacturing steps of the organic electroluminescent device taking R-ODPPXZ with the doping concentration of 3wt% as a light-emitting layer are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 3wt% R-ODPPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100)nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device having light-emitting layer of R-ODPPXZ with doping concentration of 3wt%
Applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The luminescent property of the organic electroluminescent device is measured under the condition that the external direct current voltage is changed; the maximum external quantum efficiency of the device is 12.9%.
(IV) preparation and Performance evaluation of an organic electroluminescent device having a light-emitting layer of R-ODPPXZ with a doping concentration of 15wt%
The manufacturing steps of the organic electroluminescent device with the light-emitting layer of R-ODPPXZ with the doping concentration of 15wt% are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 15wt% R-ODPPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device having light-emitting layer of R-ODPPXZ with doping concentration of 15wt%
Applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The luminescent property of the organic electroluminescent device is measured under the condition that the external direct current voltage is changed; the maximum external quantum efficiency of the device is 7.6%.
The circularly polarized organic electroluminescent device prepared by using the chiral orange red photothermal activation delayed fluorescence material of the R-ODPPXZ provided by the invention has high external quantum efficiency, higher luminous efficiency and low open-circuit voltage, and is an excellent OLED material.
(V) preparation and performance evaluation of organic electroluminescent device with light-emitting layer of R-ODQPXZ with doping concentration of 10wt%
The manufacturing steps of the organic electroluminescent device with the light-emitting layer as R-ODQPXZ with the doping concentration of 10wt% are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 10wt% R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device having light-emitting layer of R-ODQPXZ with doping concentration of 10wt%
Applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The luminescent property of the organic electroluminescent device is measured under the condition that the external direct current voltage is changed; the maximum external quantum efficiency of the device is 18.0%.
(VI) preparation and Performance evaluation of an organic electroluminescent device in which R-ODQPXZ with a doping concentration of 20wt% is a light-emitting layer
The manufacturing steps of the organic electroluminescent device with the light-emitting layer of R-ODQPXZ with the doping concentration of 20wt% are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 20wt% R-ODQPXZ (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of organic electroluminescent device having light-emitting layer of R-ODQPXZ with doping concentration of 20wt%
Applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The luminescent property of the organic electroluminescent device is measured under the condition that the external direct current voltage is changed; the maximum external quantum efficiency of the device is 20.7%.
The organic electroluminescent device based on the material can emit yellow or orange-red fluorescence (lambda =548 or 600 nm), the external quantum efficiency EQE of the device is as high as 28.3 percent and 20.3 percent, and the asymmetric factor is 6.0 multiplied by 10-4And 2.4X 10-3And has the advantages of low driving voltage, good luminous stability and the like. The chiral thermally-activated delayed fluorescent material and the organic electroluminescent device based on the same have wide application prospects in the fields of 3D display, information storage and processing, circular polarization light-emitting lasers, biological probes, photocatalytic asymmetric synthesis and the like.
The compound is prepared by the following steps of mixing R/S-18, 21-bis (9, 9-dimethylacridin-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ] dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4] Dioxin [2,3-i ] phenazine (R/S-OBPDMAC) to:
Figure 614045DEST_PATH_IMAGE015
the reaction formula is as follows:
Figure 92431DEST_PATH_IMAGE016
the reaction is as follows:
0.45 g (3.12 mmol) of 4, 5-difluorobenzene-1, 2-diamine and 1.12 g (3.06 mmol) of 3, 6-dibromo-9, 10-phenanthrenequinone are added into a 150 mL three-neck flask, 100 mL of absolute ethyl alcohol is added as a solvent, the mixture is stirred under the protection of nitrogen, the mixture reacts for 2 hours at the temperature of 80 ℃, then the reaction solution is filtered, and a filter cake is recrystallized by the absolute ethyl alcohol to obtain 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine as a light yellow solid, wherein the yield is 95%.
A150 mL three-necked flask was charged with 0.50 g (1.05 mmol) of 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine, 0.50 g (2.38 mmol) of 9, 9-dimethylacridine, 0.41 g (4.27 mmol) of sodium tert-butoxide, 0.016 g (0.055 mmol) of tri-tert-butylphosphine tetrafluoroborate, 0.05 g (0.055 mmol) of tris (dibenzylideneacetone) dipalladium (0), 50 mL of toluene was added as a solvent, and the mixture was heated at 100 ℃ under nitrogen atmosphere for reaction; after the reaction is finished, extracting with 100 mL of dichloromethane, combining organic phases, performing suction filtration, and separating and purifying the product by adopting a column chromatography (petroleum ether/dichloromethane with the volume ratio of 1: 2) method to obtain an orange solid 3, 6-bis (9, 9-dimethylacridin-10-yl) -11, 12-difluorodibenzo [ a, c ] phenazine with the yield of 80%.
A150 mL three-necked flask was charged with 0.50 g (0.68 mmol) of 3, 6-bis (9, 9-dimethylacridin-10-yl) -11, 12-difluorodibenzo [ a, c ] phenazine, 0.22 g (0.75 mmol) of R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol and 0.35 g (2.53 mmol) of potassium carbonate, and then DMF (50 mL) was added as a solvent, and the reaction was stirred at 70 ℃ under the protection of nitrogen; after the reaction is finished, extracting with 100 mL of dichloromethane, combining organic phases and carrying out suction filtration; the product is separated and purified by a column chromatography (petroleum ether/dichloromethane, volume ratio is 1: 2) method to obtain a final product R/S-18, 21-bis (9, 9-dimethylacridin-10-yl) -3,4,5,6,7,8,9, 10-octahydrodibenzo [ a, c ] dinaphtho [2', 1': 5,6, 1', 2': 7,8] [1,4] Dioxin [2,3-i ] phenazine, at a yield of 70%.
The eluent for column chromatography is prepared by mixing one of organic solvents with small polarity such as petroleum ether, isopentane, n-pentane, hexane, cyclohexane and the like with another organic solvent with large polarity, such as dichloromethane, trichloromethane, ethyl acetate, ethanol and the like, and the volume ratio of the eluent is 1: 2 to 5.
The selection of R/S-5,5',6,6',7,7',8,8' -octahydrobinaphthol can lead to the corresponding chiral product. FIG. 16 shows the nuclear magnetic hydrogen spectrum of the compound R-OBPDMAC obtained as described above; FIG. 17 is a nuclear magnetic carbon spectrum of the compound R-OBPDMAC obtained as described above; FIG. 18 is a mass spectrum of the compound R-OBPDMAC obtained as described above. The structure detection of the compound R-OBPDMAC is as follows:
1H NMR (400 MHz, CDCl3) δ 9.67 (d, J = 8.5 Hz, 2H), 8.41 (d, J = 1.8 Hz, 2H), 8.15 (s, 2H), 7.73 (dd, J = 8.5, 1.8 Hz, 2H), 7.52-7.40 (m, 4H), 7.18-7.10 (m, 4H), 6.99-6.83 (m, 8H), 6.39-6.24 (m, 4H), 2.94-2.72 (m, 6H), 2.51 (dt, J = 17.6, 5.8 Hz, 2H), 1.84 (dd, J = 12.8, 6.2 Hz, 6H), 1.77 (t, J= 10.4 Hz, 2H), 1.71 (s, 12H)；
13C NMR (101 MHz, CDCl3) δ 153.19, 151.02, 143.30, 141.35, 140.68, 140.58, 136.98, 135.49, 133.92, 131.61, 130.19, 130.11, 130.02, 129.18, 126.47, 126.04, 125.52, 120.76, 119.74, 118.65, 114.05, 36.01, 31.70, 29.39, 27.75, 22.80, 22.67；MALDI-TOF MS (ESI, m/z) calcd for C70H56N4O2 [M+]: 984.44, Found: 984.827。
comparative application example
(I) preparation and performance evaluation of organic electroluminescent device with R-OBPDMAC (rare-earth-oxygen-boron-doped-manganese-oxygen-doped-manganese) with doping concentration of 7wt% as light-emitting layer
The manufacturing steps of the organic electroluminescent device taking R-OBPDMAC with the doping concentration of 7wt% as a luminescent layer are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 7wt% R-OBPDMAC (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of an organic electroluminescent device in which R-OBPDMAC with a doping concentration of 7wt% was a light-emitting layer:
applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The luminescent property of the organic electroluminescent device is measured under the condition that the external direct current voltage is changed; the maximum external quantum efficiency of the device is 13.0%.
(II) preparation and performance evaluation of organic electroluminescent device with light-emitting layer of R-OBPDMAC with doping concentration of 15wt%
The manufacturing steps of the organic electroluminescent device taking R-OBPDMAC with the doping concentration of 15wt% as a luminescent layer are as follows:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP: 15wt% R-OBPDMAC (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Performance evaluation of an organic electroluminescent device in which R-OBPDMAC having a doping concentration of 15wt% is a light emitting layer:
applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The luminescent property of the organic electroluminescent device is measured under the condition that the external direct current voltage is changed; the maximum external quantum efficiency of the device is 10.5%.
(III) preparation and performance evaluation of organic electroluminescent device without doped luminescent layer
The organic electroluminescent device without the light-emitting layer is prepared by the following steps:
(1) pretreatment of the glass anode: selecting a glass substrate (3 x 3 mm) with an Indium Tin Oxide (ITO) film pattern as a transparent electrode; cleaning the glass substrate with ethanol, and then treating with UV-ozone to obtain a pretreated glass substrate;
(2) vacuum evaporation: vacuum evaporation of each layer is carried out on the pretreated glass substrate by a vacuum evaporation method, the treated glass substrate is put into a vacuum evaporation cavity, and the vacuum degree is less than or equal to 2 multiplied by 10-4Pa, the structure of the device is as follows: ITO/HAT-CN (10 nm)/TAPC (45 nm)/TCTA (5 nm)/CBP (20 nm)/B3PYMPM (45 nm)/Liq (2 nm)/Al (100 nm); specifically, evaporation of each layer is a conventional technology;
(3) packaging the device: sealing the prepared organic electroluminescent device in a nitrogen atmosphere glove box with the water oxygen concentration of less than 1 ppm, covering the film-forming substrate by using a sealing cover with epoxy type ultraviolet curing resin glass, and performing ultraviolet curing for sealing; the specific packaging is conventional.
Evaluation of the performance of the organic electroluminescent device not doped with the light-emitting layer:
applying direct current to the prepared organic electroluminescent device, and evaluating the luminescence property by using a PhotoResearch PR655 luminance meter; the current-voltage characteristics were measured using a computer controlled Keithley model 2400 digital source meter. The luminescent property of the organic electroluminescent device is measured under the condition that the external direct current voltage is changed; the maximum external quantum efficiency of the device is 2.7%.
It is obvious that the above description of the embodiments is only intended to assist the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (3)

1. A preparation method of a chiral thermal activation delayed fluorescence material is characterized by comprising the following steps: the chiral thermal activation delayed fluorescence materials R1 and S1 are prepared by reacting 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine) and 5,5',6,6',7,7',8,8' -octahydrobinaphthol serving as raw materials; or 10,10' - ((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) and 5,5',6,6',7,7',8,8' -octahydrobinaphthol are used as raw materials to prepare the chiral thermal activation delayed fluorescence materials R2 and S2 through reaction, wherein the chemical structural formulas of the chiral thermal activation delayed fluorescence materials are as follows:
Figure DEST_PATH_IMAGE001
the molar ratio of the 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenoxazine) to the 5,5',6,6',7,7',8,8' -octahydrobinaphthol is 1: 0.8-1.1; the molar ratio of 10,10' - (((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine) to 5,5',6,6',7,7',8,8' -octahydrobinaphthol is 1: 0.8-1.1, the reaction is carried out in the presence of alkali and under the protection of nitrogen, the reaction temperature is 40-100 ℃, and the reaction time is 12-24 hours.
2. The method for preparing the chiral thermal activation delayed fluorescence material according to claim 1, wherein the chiral thermal activation delayed fluorescence material is prepared by taking 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenazine and 10H-phenazine as raw materials and reacting to obtain 10,10' - (11, 12-difluorodibenzo [ a, c ] phenazine-3, 6-diyl) bis (10H-phenazine); the method comprises the steps of taking 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline and 10H-phenoxazine as raw materials, reacting to obtain 10,10' - (((6, 7-difluoroquinoxaline-2, 3-diyl) bis (4, 1-phenylene)) bis (10H-phenoxazine), wherein the molar ratio of the 3, 6-dibromo-11, 12-difluorodibenzo [ a, c ] phenoxazine to the 10H-phenoxazine is 1: 2.2-2.6, the molar ratio of the 2, 3-bis (4-bromophenyl) -6, 7-difluoroquinoxaline to the 10H-phenoxazine is 1: 2.2-2.6, and the reaction is carried out in the presence of a palladium catalyst, wherein the reaction temperature is 90-130 ℃, and the reaction time is 20-28H.
3. The method for preparing the chiral thermally activated delayed fluorescence material according to claim 1, wherein after the reaction is completed, the reaction solution is extracted, then the organic phases are combined and filtered, and the chiral photothermal activated delayed fluorescence material is obtained.
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