CN115710280B - Dithienophenazine receptor-based compounds, synthesis method and application thereof - Google Patents
Dithienophenazine receptor-based compounds, synthesis method and application thereof Download PDFInfo
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- CN115710280B CN115710280B CN202211378894.9A CN202211378894A CN115710280B CN 115710280 B CN115710280 B CN 115710280B CN 202211378894 A CN202211378894 A CN 202211378894A CN 115710280 B CN115710280 B CN 115710280B
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- phenyl
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- diphenyl
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- 230000005693 optoelectronics Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical class O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
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- 238000007747 plating Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 239000012312 sodium hydride Substances 0.000 description 1
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- 238000010183 spectrum analysis Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a compound based on a dithienophenazine receptor, which takes the dithienophenazine receptor as a parent body and contains one or more substituents of nitrogen-containing aryl, aromatic phosphine oxide groups and cyano groups as donors. The method can improve the carrier transmission capacity, weaken the quenching effect, block the conjugate extension and ensure the emission wavelength of the material, thereby obtaining a red light thermal excitation delayed fluorescent material with stable thermal performance and electrical performance.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a compound based on a dithienophenazine receptor, a synthesis method and application thereof.
Background
Organic electroluminescent diodes (Organic Light Emitting Diodes, OLEDs) have the advantages of low driving voltage, fast response, wide viewing angle, ultra-thin, flexible display, etc., and have been widely used for display screens for smart phones, watches, computers, and other devices. The first generation of organic electroluminescent materials are fluorescent materials, and because the materials only emit light by using singlet excitons, the internal quantum efficiency can reach 25% theoretically. The second generation electroluminescent material is a phosphorescence material based on heavy metal complex, and can realize 100% internal quantum efficiency by utilizing singlet state and triplet state exciton luminescence at the same time; however, the expensive cost and environmental pollution of metal complexes remain unsolved problems.
The advent of third generation thermally excited delayed fluorescence (Thermally Activated Delayed Fluorescence, TADF) materials has provided new design considerations to researchers. The TADF material is characterized in that triplet excitons can be converted into singlet excitons capable of radiation transition through reverse intersystem crossing under the action of heat assistance, so that the light emission by utilizing the singlet excitons and the triplet excitons is realized, and the internal quantum efficiency of 100% is realized.
Most TADF luminescent molecules are of the pure organic Donor (Donor) -Acceptor (acceptors) structure. Using twisted donor (D) and acceptor (A) configurations to achieve smaller singlet-triplet energy minima (ΔE) ST ) And TADF characteristics because well-separated Highest Occupied Molecular Orbital (HOMO) and lowest unoccupied molecular orbital can minimize Δe ST . Fast reverse intersystem crossing (RISC) is achieved, thereby utilizing triplet excitons to emit light and reducing quenching of triplet excitons. Compared with fluorescence and phosphorescence technologies, the TADF material has the advantages of resource sustainability, low cost and environmental friendliness. However, effective singlet irradiation requires sufficient overlap of the initial and final states. Thus, a small ΔE ST And high photoluminescence quantum yield (PLQY) are one of the key contradictions in the construction of efficient TADF materials.
The luminous efficiency of red TADF molecules is extremely sensitive to doping concentration, and the adoption of an undoped luminous layer structure results in an efficiency loss of up to 80%. In addition to the more polar nature of the molecule itself, there is a more severe non-radiative transition process itself. Currently, few undoped red TADF devices can have External Quantum Efficiencies (EQEs) in excess of 10%. Thus, the optoelectronic properties of the red TADF molecules themselves are a key bottleneck limiting the performance enhancement of undoped red TADF devices.
Four strategies are provided for improving the Photoluminescence (PL) and Electroluminescence (EL) performance of red TADF emitters: (1) Has reasonable molecular accumulation and intermolecular interaction to achieve both charge transfer and quenching inhibition; (2) The radiation process has absolute advantages over the non-radiation process to obtain high luminous efficiency; (3) RISC efficiency approaches 100% to obtain thermodynamic advantages of delayed fluorescence; (4) Rapid charge recombination and exciton radiation to avoid quenching due to exciton accumulation.
To achieve a red TADF material, it is often desirable to further enhance the interaction between the donor and acceptor, while stronger interactions tend to increase the polarity of the material, enhancing intermolecular interactions, leading to severe concentration quenching. Therefore, how to obtain the high-efficiency red light TADF material, and develop a luminescent material meeting the requirements are difficult scientific problems.
Disclosure of Invention
In order to solve the above problems, the present invention provides a compound containing a dithienophenazine receptor. In the compound, dithienophenazine is taken as a receptor, nitrogen-containing aryl, aromatic phosphine oxide groups and cyano groups are modified as donors, the carrier transmission capacity is improved, the quenching effect is weakened, the conjugated extension is blocked, and the emission wavelength of the material is ensured, so that a red light thermal excitation delayed fluorescent material with stable thermal performance and electrical performance is obtained, and the invention is completed.
It is an object of a first aspect of the present invention to provide a dithienophenazine acceptor-based compound in which the dithienophenazine acceptor is used as a parent and one or more substituents selected from the group consisting of a nitrogen-containing aryl group, an aromatic phosphine oxide group and a cyano group are used as a donor.
The second aspect of the invention also provides a preparation method of the dithiophene-phenazine receptor-based compound. According to the method, 5, 6-dihalogenated benzo [ c ] [1,2,5] thiadiazole is used as a starting material to prepare an o-aminobenzene compound, then the o-aminobenzene compound is combined with a benzodithiophene-4, 5-diketone compound to form a ring, and a nitrogen-containing aryl group, an aromatic phosphine oxide group or a cyano group is connected to obtain a compound based on a dithienophenazine receptor.
The anthranilic compound has the following structure:
wherein X is 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinyloxy groups, preferably selected from diphenylaminophenyl or diphenylphosphinyloxy.
The benzodithiophene-4, 5-dione compound is benzodithiophene-4, 5-dione or 2, 7-dibromobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione.
The method comprises the following steps:
step 1, preparing an o-aminobenzene compound by using 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole;
step 2, carrying out cyclization reaction on an o-aminobenzene compound and a benzodithiophene-4, 5-diketone compound to obtain an intermediate;
and 3, reacting the intermediate with an aromatic amine compound, an aromatic phosphine compound or a cyano compound to obtain a compound based on a dithienophenazine receptor.
In a third aspect, the present invention is directed to the use of the dithienophenazine acceptor-based compounds for the preparation of electroluminescent red devices as luminescent layer materials.
It is an object of a fourth aspect of the present invention to provide an electroluminescent red device whose luminescent layer material comprises the dithienophenazine acceptor-based compound.
The invention has the following beneficial effects:
(1) The dithiophene-phenazine receptor-based compound provided by the invention is used as a red light thermal excitation delayed fluorescent material, and the introduced aromatic amine groups are strong electron donating groups, so that the carrier transmission capacity can be improved, reasonable molecular accumulation state and intermolecular acting force can be obtained by utilizing the steric effect of the aromatic phosphine oxide groups, and meanwhile, the conjugated extension is blocked by utilizing the phosphine oxide groups, so that the quenching effect is weakened.
(2) The diphenyl phosphorus oxygen group has proper electron-withdrawing capability, strong steric hindrance effect and hydrogen bond capability, can effectively red shift wavelength, and reduces delta E ST Concentration quenching is inhibited, and TADF efficiency is improved.
(3) The invention has reasonable molecular accumulation and intermolecular interaction by designing the molecular structure so as to ensure electron transmission and inhibit concentration quenching, thereby being capable of obtaining the red light TADF material.
(4) The maximum external quantum efficiency of the electroluminescent red light device prepared by the method can reach 23.7%, and the luminous wavelength can reach 660nm, so that the electroluminescent red light device has good performance.
Drawings
FIG. 1 shows an ultraviolet absorption spectrum and a photoluminescence spectrum (fluorescence spectrum) of compound 1 in example 1 of the present invention;
FIG. 2 shows a thermogram of compound 1 in example 1 of the present invention;
FIG. 3 shows an ultraviolet absorption spectrum and a photoluminescence spectrum (fluorescence spectrum) of compound 5 in example 5 of the present invention;
FIG. 4 shows a thermogram of compound 5 in example 5 of the present invention;
fig. 5 shows an electroluminescence spectrum of the electroluminescent red light device 1 in example 1 of the present invention;
fig. 6 shows an electroluminescence spectrum of the electroluminescent red light device 2 in example 2 of the present invention;
fig. 7 shows an electroluminescence spectrum of the electroluminescent red light device 3 in example 3 of the present invention;
fig. 8 shows an electroluminescence spectrum of the electroluminescent red light device 4 in example 4 of the present invention;
FIG. 9 shows an electroluminescence spectrum of the electroluminescent red light device 5 in example 5 of the present invention;
fig. 10 shows an electroluminescence spectrum of an electroluminescent red light device 6 in example 6 of the present invention;
fig. 11 shows an electroluminescence spectrum of the electroluminescence device 7 in example 7 of the present invention;
FIG. 12 shows an electroluminescence spectrum of an electroluminescent red light device 8 in example 8 of the present invention;
FIG. 13 is a graph showing the voltage-luminance relationship of the electroluminescent red device 5 in example 5 of the present invention;
FIG. 14 shows the luminance versus current efficiency for the electroluminescent red device 5 in example 5 of the present invention;
FIG. 15 shows the luminance-power efficiency relationship of the electroluminescent red device 5 in example 5 of the present invention;
fig. 16 shows a luminance-external quantum efficiency relationship of the electro-red light-emitting device 5 in example 5 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The compound based on the dithiophene-oxazine receptor provided by the invention takes the dithiophene-oxazine as the receptor, and modifies nitrogen-containing aryl, aromatic phosphine oxide groups and cyano groups as donors, so that a red light thermal excitation delayed fluorescent material is obtained. Compared with the existing thermal excitation delayed fluorescent material, the carrier transmission capability of the compound is improved, the quenching effect is further weakened, the aromatic phosphine oxide group can also block conjugate extension, the emission wavelength of the material is ensured, and the electroluminescent device obtained by the compound has good red light luminescence performance.
In a first aspect, the present invention provides a compound based on a dithienophenazine acceptor, wherein the dithienophenazine acceptor is used as a parent body, and one or more substituents selected from a nitrogen-containing aryl group, an aromatic phosphine oxide group and a cyano group are used as a donor.
The compounds have the general formula:
wherein X is 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphine oxide groups, preferably aryl-substituted aminophenyl,Phenylphosphinyloxy, diphenylphosphinyloxy or triphenylphosphine yloxy, more preferably selected from diphenylaminophenyl or diphenylphosphinyloxy.
R 1 、R 2 Each independently selected from hydrogen, cyano, nitrogen-containing aryl, or aromatic phosphine oxide groups, preferably hydrogen, cyano, aryl-substituted aminophenyl, phenylphosphinoxide, diphenylphosphinoxide, or triphenylphosphine oxide, more preferably hydrogen, cyano, diphenylaminophenyl, or diphenylphosphinoxide.
Preferably, the dithiophene-oxazine receptor-based compound is selected from one of compounds 1 to 8, and compounds 1 to 8 are specifically as follows:
the dithiophene-phenazine receptor-based compound provided by the invention is used as a dithiophene-phenazine red light thermal excitation delayed fluorescent material, and the introduced nitrogen-containing aryl group, such as a triphenylamine group, is a strong electron donating group, so that the carrier transmission capacity can be improved, and the Intramolecular Charge Transfer (ICT) capacity and RISC efficiency can be improved. The cyano group has strong electron withdrawing capability, and the introduction of the cyano group can lead the spectrum of the compound of the system to be obviously red-shifted. The steric hindrance effect of the aromatic phosphine oxide group can obtain reasonable molecular stacking state and intermolecular acting force so as to weaken quenching effect, improve photoluminescence quantum yield of the aromatic phosphine oxide group serving as a thermal excitation delayed fluorescence luminescent material, realize improvement of luminescent efficiency of a device and ensure emission wavelength of the material.
In addition, the aromatic phosphine oxide group has proper electron withdrawing capacity, strong steric hindrance effect and hydrogen bond forming capacity, can effectively red shift wavelength and reduce delta E ST Concentration quenching is inhibited, and TADF efficiency is improved. Therefore, the molecular configuration, the electrical property and the like of the material can be adjusted by introducing the phosphine oxide group into the donor-acceptor structure so as to realizeThe high-efficiency red light TADF material is realized.
In addition, the dithiophene-phenazine receptor-based compound provided by the invention also has good thermal stability, so that the stability of the device is improved. The material is used as a guest material of the light-emitting layer, and the current efficiency and the power efficiency of the electroluminescent device are effectively improved.
In view of the numerous advantages of the dithienophenazine acceptor receptor for improving the charge transport capacity of the material and the above-mentioned diphenylphosphorus oxy groups, compounds 1-4 are preferred, which have higher brightness and external quantum efficiency relative to the current common TADF red light molecules. With the increase of the number of diphenyl phosphorus oxygen groups in the compounds based on the dithiophene-oxazine receptor, preferably compounds 5 to 8, the emission wavelength can be red shifted and higher electroluminescent performance can be achieved.
The second aspect of the invention also provides a preparation method of the dithiophene-phenazine receptor-based compound. According to the method, 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole is used as a starting material to prepare an o-aminobenzene compound, and then the o-aminobenzene compound is cyclized with a benzodithiophene-4, 5-dione compound to obtain a compound based on a dithiophene-phenazine receptor; or, 5, 6-dihalogenated benzo [ c ] [1,2,5] thiadiazole is used as a starting material to prepare an o-aminobenzene compound, then the o-aminobenzene compound is combined with a benzodithiophene-4, 5-diketone compound to be connected with a nitrogen-containing aryl group, an aromatic phosphine oxide group or a cyano group, so as to obtain the compound based on a dithiophene-phenazine receptor.
The anthranilic compound has the following structure:
wherein X is 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinyloxy groups, preferably selected from aryl-substituted aminophenyl, phenylphosphinyloxy, diphenylphosphinyloxy or triphenylphosphine yloxy, more preferably diphenylaminophenyl or diphenylphosphinyloxy.
Preferably, the o-aminobenzene compound is 4-nitrogenous aryl-5-aromatic phosphinyloxy o-phenylenediamine or 4, 5-di-nitrogenous aryl o-phenylenediamine, wherein the nitrogenous aryl is preferably aryl substituted aminophenyl, the aromatic phosphinyloxy is preferably phenylphosphinyloxy, diphenylphosphinyloxy or triphenylphosphine oxy, more preferably, the o-aminobenzene compound is 4- (4-diphenylamino) phenyl-5-diphenylphosphinyloxy o-phenylenediamine or 4, 5-di (4-diphenylamino) phenyl-o-phenylenediamine.
The benzodithiophene-4, 5-dione compound is benzodithiophene-4, 5-dione or 2, 7-dihalogenated benzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione, and the halogenation is bromo, iodo or chloro, preferably bromo.
The method comprises the following steps:
step 1, preparing the o-aminobenzene compound by using 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole.
In the 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole, the halo is bromo, iodo or chloro, preferably bromo.
The 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole is reacted with an aromatic amine boron compound to obtain 5, 6-di-nitrogen-containing arylbenzo [ c ] [1,2,5] thiadiazole or 5-nitrogen-containing aryl-6-halogenobenzo [ c ] [1,2,5] thiadiazole.
The reaction with aromatic amine boron compound is carried out for 10-14h at 100-120 ℃ in the presence of palladium catalyst and solvent under alkaline condition. The solvent is one or more of aromatic hydrocarbon solvents, preferably toluene and/or xylene, and more preferably toluene.
The molar ratio of the 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole to the aromatic amine boron compound is 1 (2-2.5) or 1 (0.8-1.0), and is preferably 1:2 or 1:1.
The 5, 6-di-nitrogen aryl benzo [ c ] [1,2,5] thiadiazole is reduced to obtain 4, 5-di-nitrogen aryl o-phenylenediamine. Preferably, the reduction is carried out by sodium borohydride in the presence of a solvent and a cobalt salt catalyst (e.g., cobalt chloride) at 70-90 ℃ for 40-55h. The solvent is selected from one or more of alcohol solvents, preferably one or more of methanol, propanol and isopropanol, more preferably methanol.
The 5-nitrogenous aryl-6-halogenated benzo [ c ] [1,2,5] thiadiazole reacts with an aromatic phosphine compound, is oxidized by hydrogen peroxide to obtain 5-nitrogenous aryl-6-aromatic phosphine oxide benzo [ c ] [1,2,5] thiadiazole, and is reduced to obtain 4-nitrogenous aryl-5-aromatic phosphine oxide o-phenylenediamine.
The 5-nitrogenous aryl-6-halogenated benzo [ c ] [1,2,5] thiadiazole is reacted with an aromatic phosphine compound, and the reaction is carried out for 10-14h at 125-145 ℃ in the presence of a palladium catalyst and a solvent. The solvent is selected from one or more of amide solvents, preferably N, N-dimethylformamide and/or N, N-dimethylacetamide, more preferably N, N-dimethylformamide.
The reduction is carried out by sodium borohydride in the presence of solvent and cobalt salt catalyst (such as cobalt chloride) and the reaction is carried out for 40-55h at 70-90 ℃. The solvent is selected from one or more of alcohol solvents, preferably one or more of methanol, propanol and isopropanol, more preferably methanol.
The aromatic amine boron compound is selected from aryl substituted aminobenzene-4-boric acid pinacol ester or aryl substituted aminobenzene-4-boric acid, preferably triphenylamine-4-boric acid pinacol ester or triphenylamine-4-boric acid, and more preferably triphenylamine-4-boric acid pinacol ester. The nitrogen-containing aryl group is preferably an aryl-substituted aminophenyl group, more preferably a 4-diphenylamino-phenyl group.
The aromatic phosphine compound is selected from phenylphosphine, diphenylphosphine or triphenylphosphine, preferably diphenylphosphine. The aromatic phosphinyloxy group is selected from phenylphosphinyloxy, diphenylphosphinyloxy or triphenylphosphine yloxy, preferably diphenylphosphinyloxy.
And step 2, carrying out cyclization reaction on the o-aminobenzene compound and the benzodithiophene-4, 5-diketone compound to obtain an intermediate.
In one embodiment of the invention, the benzodithiophene-4, 5-dione compound is benzodithiophene-4, 5-dione, the o-aminobenzene compound is 4, 5-di-nitrogen-containing aryl o-phenylenediamine or 4-nitrogen-containing aryl-5-aromatic phosphine oxide o-phenylenediamine, and the compound 1 or the compound 5 is obtained through reaction.
In another embodiment of the invention, the benzodithiophene-4, 5-dione compound is 2, 7-dihalobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione, and the anthranilic compound is 4, 5-di-nitrogen-containing aryl-o-phenylenediamine or 4-nitrogen-containing aryl-5-aromatic phosphinyloxy-o-phenylenediamine, and the intermediate is obtained by reaction.
The intermediate is as follows:
wherein X is 0 Chlorine, iodine or bromine, preferably bromine; x is X 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinyloxy groups, preferably aryl-substituted aminophenyl, phenylphosphinyloxy, diphenylphosphinyloxy or triphenylphosphine yloxy, more preferably diphenylaminophenyl or diphenylphosphinyloxy. More preferably X 1 、X 2 Are each diphenylaminophenyl or X 1 Is diphenyl aminophenyl, X 2 Is diphenylphosphinyloxy.
The cyclization reaction is carried out in a carboxylic acid solvent at 110-130 ℃ for 10-14h. The carboxylic acid solvent is selected from one or more of acetic acid, propionic acid and formic acid, preferably acetic acid. The molar ratio of the o-aminobenzene compound to the benzodithiophene-4, 5-dione compound is (1.0-2.0): 1, preferably (1.2-1.5): 1, and more preferably 1.5:1.
And 3, reacting the intermediate with an aromatic amine compound, an aromatic phosphine compound or a cyano compound to obtain a compound based on a dithienophenazine receptor.
The aromatic amine compound is selected from aryl substituted aminobenzene-4-boric acid pinacol ester or aryl substituted aminobenzene-4-boric acid, preferably triphenylamine-4-boric acid pinacol ester or triphenylamine-4-boric acid. The intermediate is reacted with an aromatic amine compound to give a compound based on the dithienophenazine receptor, in which case,wherein R is 1 、R 2 Are nitrogen-containing aryl groups, preferably amino aryl groups, more preferably diphenylaminophenyl groups, such as compound 4, compound 8.
The intermediate reacts with aromatic amine boron compound, and the intermediate reacts for 10-14h at 100-120 ℃ in the presence of palladium catalyst and solvent under alkaline condition. The solvent is one or more of aromatic hydrocarbon solvents, preferably toluene and/or xylene, and more preferably toluene.
The aromatic phosphine compound is phenylphosphine, diphenylphosphine or triphenylphosphine, preferably diphenylphosphine. The intermediate reacts with aromatic phosphine compounds, and is oxidized by hydrogen peroxide to obtain compounds based on dithiophene-phenazine receptors,wherein R is 1 、R 2 All aromatic phosphinyloxy, preferably phenylphosphinyloxy, diphenylphosphinyloxy or triphenylphosphine yloxy, more preferably diphenylphosphinyloxy, such as compound 2, compound 6.
The intermediate reacts with aromatic phosphine compounds, the reaction is carried out for 10 to 14 hours at the temperature of 125 to 145 ℃ in the presence of a palladium catalyst and a solvent, hydrogen peroxide is added for oxidation after the reaction is finished, and the compound based on a dithienophenazine receptor is obtained after post-treatment. The solvent is selected from one or more of amide solvents, preferably N, N-dimethylformamide and/or N, N-dimethylacetamide, more preferably N, N-dimethylformamide.
The cyano compound is selected from metal cyanide, preferably one or more of cuprous cyanide, sodium hydride and potassium hydride, more preferably cuprous cyanide. The intermediate is reacted with a cyano compound to give a compound based on the dithienophenazine acceptor, in which case,wherein R is 1 、R 2 Are cyano groups, such as compound 3, compound 7.
The intermediate is reacted with a cyano compound in the presence of a solvent at 135-145 ℃ for 10-14h. The solvent is selected from one or more of amide solvents, preferably N, N-dimethylformamide and/or N, N-dimethylacetamide, more preferably N, N-dimethylformamide.
The synthesis route of the compound based on the dithiophene-phenazine receptor is reasonable in design, the synthesis method is easy to carry out, and a target product can be stably obtained.
In a third aspect the present invention provides the use of a dithienophenazine acceptor-based compound according to the first aspect as a light-emitting layer material for the preparation of an electroluminescent red device.
The brightness of the electroluminescent red light device is 7500-26000 cd.m -2 Preferably 15000-25000 cd.m -2 More preferably 16000-19000 cd.m -2 。
The external quantum efficiency of the electroluminescent red light device is 5% -24%, preferably 16% -19%.
The electroluminescent wavelength of the electroluminescent red light device is 580-660nm, preferably 600-650nm, more preferably 630-640nm.
In a fourth aspect the invention provides an electroluminescent red device comprising a luminescent layer material comprising said dithiophene-based compound, preferably compound 1-compound 8, more preferably compound 5-compound 8.
The electroluminescent red light device further comprises a conductive anode layer, a hole injection layer, a hole transport layer, an electron injection layer and a cathode conductive layer.
The invention provides a preparation method of a light-emitting device with the dithiophene-phenazine receptor-based compound as a light-emitting layer material, which specifically comprises the following steps:
1. preparing a conductive anode layer;
the conductive anode layer is prepared on a substrate layer. The conductive anode layer is selected from tin oxide conductive glass (ITO), transparent conductive polymers such as polyaniline, translucent metals such as Au, preferably ITO or translucent metals, more preferably ITO. Preferably, the conductive anode layer is evaporated by vacuum evaporation.
Preferably, the vacuum degree of vacuum evaporation is 1×10 -6 The evaporation rate is set to 0.1-0.3 nm/s, the evaporation material is indium tin oxide on the glass or plastic substrate, and the anode conductive layer with the thickness of 3-20 nm is preferably 4-15 nm, more preferably 5-10 nm, such as 6nm.
Preferably, the following hole injection layer, hole transport layer, hole blocking layer, light emitting layer, electron transport layer, electron injection layer, and cathode conductive layer are prepared using a vacuum evaporation method.
2. Preparing a hole injection layer;
The hole injection layer is vapor-deposited on the anode conductive layer to a thickness of 4 to 16nm, preferably 4 to 12nm, more preferably 4 to 8nm, such as 6nm.
The hole injection layer material is selected from molybdenum oxide or poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate (PEDOT: PSS), preferably molybdenum oxide, more preferably molybdenum oxide, such as MoO 3 。
3. Preparing a hole transport layer;
the hole transport layer is vapor deposited on the hole injection layer to a thickness of 25 to 75nm, preferably 35 to 65nm, more preferably 45 to 55nm, such as 50nm.
The hole transport layer material is selected from one or more of arylamine compounds and carbazole compounds, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 9' - (1, 3-phenyl) di-9H-carbazole (mCP), and is preferably NPB.
4. Preparing a hole blocking layer;
evaporating a hole blocking layer on the hole transport layer, wherein the evaporating thickness is 2-10nm, preferably 3-7nm, more preferably 5nm;
the hole blocking layer material is 4,4' -tris (carbazol-9-yl) triphenylamine (TCTA) or 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), preferably TCTA.
5. Preparing a light-emitting layer;
the light-emitting layer is further evaporated on the hole blocking layer, wherein the evaporation thickness is 9-45nm, preferably 12-35nm, more preferably 15-25nm, such as 20nm.
The luminescent layer material comprises a compound based on a dithiophene-oxazine receptor, preferably 4,4' -bis (9-Carbazole) Biphenyl (CBP), and the mass fraction of the compound based on the dithiophene-oxazine receptor in the luminescent layer material is 10-30%, preferably 15-25%, such as 20%.
6. Preparing an electron transport layer;
the electron transport layer is vapor-deposited on the light-emitting layer to a thickness of 45 to 75nm, preferably 55 to 65nm, more preferably 60nm.
The electron transport layer material is selected from one or more of tris (8-hydroxyquinoline) aluminum (Alq 3), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), bis [2- ((oxo) diphenylphosphino) phenyl ] ether (DPEPO) and 1,3, 5-tris (m-pyridin-3-ylphenyl) benzene (TmPyPB), preferably TmPyPB.
7. Preparing an electron injection layer;
the electron injection layer is vapor-deposited on the electron transport layer to a thickness of 1-15nm, preferably 1-10nm, more preferably 1-5nm, such as 1nm.
The electron injection layer material is selected from lithium tetra (8-hydroxyquinoline) boron (LiBq) 4 ) Or LiF, preferably LiF.
8. And preparing a cathode conducting layer, and packaging to obtain the thermal excitation delayed fluorescence electroluminescent device.
The cathode conductive layer is evaporated on the electron injection layer, and the thickness of the evaporated layer is 60-130nm, preferably 70-120nm, more preferably 80-110nm, such as 100nm.
The cathode conductive layer material is selected from a single metal cathode or an alloy cathode, such as metallic Al.
Examples
Example 1
(1) 1mmol of 5, 6-dibromobenzo [ c ] [1,2,5] thiadiazole, 2mmol of triphenylamine-4-boronic acid pinacol ester, 0.05mmol of tetrakis (triphenylphosphine) palladium, 0.1mmol of tetrabutylammonium bromide, 6mmol of sodium hydroxide and 10mL of toluene were mixed and reacted at 110℃for 12h. After the reaction is finished, adding water and methylene dichloride for extraction, combining an organic layer, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of methylene dichloride and petroleum ether (the volume ratio of the methylene dichloride to the petroleum ether is 1:4) as a leaching agent to obtain 4,4' - (benzo [ c ] [1,2,5] thiadiazole-5, 6-diyl) bis (N, N-diphenyl aniline):
(2) Cobalt chloride hexahydrate 0.05mmmol, sodium borohydride 7mmol and methanol 10ml were mixed with 1mmol of 4,4' - (benzo [ c ] [1,2,5] thiadiazole-5, 6-diyl) bis (N, N-diphenylaniline) obtained in the above step, respectively, and reacted at 80℃for 48 hours. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, and performing column chromatography purification by taking a mixed solvent of dichloromethane and ethyl acetate (the volume ratio of the dichloromethane to the ethyl acetate is 10:1) as a leaching agent to obtain a reactant I:
(3) 1mmol of benzodithiophene-4, 5-dione, 2mmol of reactant I and 20mL of acetic acid were taken and mixed, and reacted at 120℃for 12 hours. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, and performing column chromatography purification by taking a mixed solvent of dichloromethane and petroleum ether (the volume ratio of the dichloromethane to the petroleum ether is 1:1) as a leaching agent to obtain a compound 1 (4, 4' - (dithieno [2,3-a:3',2' -c ] phenazine-9, 10-diyl) bis (N, N-diphenyl aniline)).
The results of compound 1 nuclear magnetic resonance test are as follows:
1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.35(s,2H),7.83(d,J＝5.2Hz,2H),7.80(d,J＝7.2Hz,2H),7.29-7.25(m,8H),7.21(d,J＝8.4Hz,4H),7.13(d,J＝7.8Hz,8H),7.04(t,J＝8.8Hz,8H).
the toluene solution of compound 1 and the film of compound 1 were tested for ultraviolet absorption spectrum and photoluminescence spectrum (fluorescence spectrum), as shown in fig. 1.
The resulting compound 1 was subjected to thermogravimetric analysis, and as shown in fig. 2, the cleavage temperature of the compound 1 was measured to be 486 ℃.
(3) An electroluminescent red light device was prepared using the obtained mixture of compound 1 and CBP (wherein, the mass fraction of compound 1 is 20%) as a guest material for a light emitting layer:
1. placing the glass substrate cleaned by deionized water into a vacuum evaporator, wherein the vacuum degree is 1 multiplied by 10 -6 mbar, evaporation rate was set to 0.1nm s -1 The vapor deposition material is Indium Tin Oxide (ITO) to obtain anode conduction with the thickness of 6nmA layer;
2. vapor plating of hole injection layer material MoO on anode conductive layer 3 Obtaining a hole injection layer with the thickness of 6 nm;
3. evaporating a hole transport layer material NPB on the hole injection layer to obtain a hole transport layer with the thickness of 50 nm;
4. evaporating a hole blocking layer material TCTA on the hole transport layer to obtain a hole blocking layer with the thickness of 5 nm;
5. evaporating a light-emitting layer on the hole blocking layer, wherein the material is a mixture of a compound 1 and CBP, and the mass fraction of the compound 1 is 20%, so that a light-emitting layer with the thickness of 20nm is obtained;
6. evaporating an electron transport layer material TmPyPB on the light-emitting layer to obtain an electron transport layer with the thickness of 60 nm;
7. evaporating an electron injection layer material LiF on the electron transport layer to obtain an electron injection layer with the thickness of 1 nm;
8. aluminum is evaporated on the electron injection layer to form a cathode conductive layer with the thickness of 100nm, and the electroluminescent red light device 1 is obtained.
The structure of the electroluminescent red light device 1 is as follows: ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 1 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The change trend of the current density of the electroluminescent red light device 1 with the voltage was tested, and it was found that the compound 1 had semiconductor characteristics with a threshold voltage of 4.2V.
Testing the change trend of the brightness of the electroluminescent red light device 1 along with the change of voltage to obtain the maximum brightness of the device reaching 24461 cd.m -2 。
Testing the change trend of the current efficiency of the electroluminescent red light device 1 along with the change of brightness to obtain the brightness of the device at 2.3 cd.m -2 When the current efficiency reaches the maximum value of 14.5 cd.A -1 。
Testing the change trend of the power efficiency of the electroluminescent red light device 1 along with the change of brightness to obtain the brightness of the device at 2.3 cd.m -2 When the power efficiency reaches the maximum value of 10.8 lm.W -1 。
Testing of external Quantum efficiency of Electrored device 1The change trend of the current density change is carried out to obtain the brightness of the device at 3.0 cd-m -2 When the maximum external quantum efficiency was 5.58%.
The electroluminescent spectrum of the electroluminescent red light device 1 is shown in fig. 5, and the electroluminescent peak of the device is at 588 nm.
Example 2
(1) Reactant I was prepared as described in example 1.
(2) 1mmol of 2, 7-dibromobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione, 2mmol of the reactant I and 20ml of acetic acid were taken and mixed and reacted at 120℃for 12 hours. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, and performing column chromatography purification by taking a mixed solvent of dichloromethane and ethyl acetate (the volume ratio of the dichloromethane to the ethyl acetate is 8:1) as a leaching agent to obtain an intermediate I.
(3) 1mmol of the intermediate I in the previous step, 0.005mmol of palladium acetate, 2mmol of sodium acetate, 2mmol of diphenylphosphine and 20mL of N, N-dimethylformamide are taken and mixed, the mixture is reacted for 12 hours at 135 ℃, and 5mmol of H is added 2 O 2 After the oxidation, adding water and dichloromethane for extraction, combining organic layers, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and methanol (the volume ratio of the dichloromethane to the methanol is 50:1) as a leaching agent to obtain a compound 2 ((9, 10-bis (4- (diphenylamino) phenyl) dithioeno [2,3-a:3',2' -c)]Phenazine-2, 5-diyl) bis (diphenylphosphine oxide)).
The results of compound 2 nuclear magnetic resonance test are as follows:
1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.529-8.423(m,2H),8.372-8.303(m,1H),8.219-8.157(m,1H),7.917-7.859(m,1H),7.848-7.792(m,2H),7.580-7.524(m,1H)，7.511-7.413(m,6H),7.010-6.946(m,4H),6.272-6.205(m,2H),1.5(s,6H)。
the compound 2 was subjected to thermogravimetric analysis, and the cleavage temperature was 462 ℃.
An electroluminescent red light device 2 was prepared as in example 1,the structure is as follows: ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 2 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The change trend of the current density of the electroluminescent red light device 2 with the voltage was tested, and it was found that the compound 2 had semiconductor characteristics with a threshold voltage of 3.70V.
Testing the change trend of the brightness of the electroluminescent red light device 2 along with the change of voltage to obtain the maximum brightness of the device reaching 18660 cd.m -2 。
Testing the change trend of the current efficiency of the electroluminescent red light device 2 along with the change of brightness to obtain the brightness of the device at 2.54 cd.m -2 When the current efficiency reaches the maximum value of 21.5 cd.A -1 。
Testing the change trend of the power efficiency of the electroluminescent red light device 2 along with the change of brightness to obtain the brightness of the device at 2.54 cd.m -2 When the current efficiency reaches the maximum value of 24.6cd.A -1 。
Testing the change trend of the external quantum efficiency of the electroluminescent red light device 2 on the change of the current density to obtain the brightness of the device at 2.54 cd.m -2 When the maximum external quantum efficiency was 16.4%.
The electroluminescent spectrum of the electroluminescent red light device 2 is shown in FIG. 6, and the electroluminescent peak of the device is 608 nm.
Example 3
(1) Intermediate I was prepared as in example 2.
(2) 1mmol of intermediate I, 5mmol of cuprous cyanide and 20mL of N, N-dimethylformamide are mixed and reacted at 140℃for 12h. Then pouring a mixed solution of 2M ferric trichloride and hydrochloric acid and dichloromethane for extraction, drying and removing an organic solvent to obtain a crude product, taking a mixed solvent of petroleum ether and dichloromethane (the volume ratio of the petroleum ether to the dichloromethane is 1:10) as a leaching agent, and performing column chromatography purification to obtain a compound 3 (9, 10-bis (4- (diphenylamino) phenyl) dithieno [2,3-a:3',2' -c ] phenazine-2, 5-dimethylnitrile).
The results of compound 3 nuclear magnetic resonance test are as follows:
1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.34(s,2H),8.25(s,2H),7.29(m,8H),7.20(d,J＝8.4Hz,4H),7.14(d,J＝7.6Hz,8H),7.06(m,8H)。
the thermal gravimetric analysis of compound 3 revealed a cleavage temperature of 445 ℃.
An electroluminescent red light device 3 was prepared according to the method of example 1, and its structure was: ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 3 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The change trend of the current density of the electroluminescent red device 3 with voltage was tested, and it was found that the compound 3 had semiconductor characteristics with a threshold voltage of 3.4V.
Testing the change trend of the brightness of the electroluminescent red light device 3 along with the change of voltage to obtain the maximum brightness of the device reaching 16233 cd-m -2 。
The change trend of the current efficiency of the electroluminescent red light device 3 along with the change of the brightness is tested, and the brightness of the device is 2.9 cd.m -2 When the current efficiency reaches the maximum value of 19.6cd.A -1 。
Testing the change trend of the power efficiency of the electroluminescent red light device 3 along with the change of brightness to obtain the brightness of the device at 2.9 cd.m -2 When the power efficiency reaches the maximum value of 18.3 lm.W -1 。
Testing the change trend of the external quantum efficiency of the electroluminescent red light device 3 on the change of the current density to obtain the brightness of the device at 2.9 cd-m -2 When the maximum external quantum efficiency was 18.8%.
The electroluminescent spectrum of the electroluminescent red light device 3 is shown in FIG. 7, from which it can be seen that the electroluminescent peak of the device is at 632 nm.
Example 4
(1) Intermediate I was prepared as in example 2.
(2) 1mmol of intermediate I, 2mmol of triphenylamine 4-borate, 0.025mmol of tetrakis (triphenylphosphine) palladium, 0.2mmol of tetrabutylammonium bromide, 6mmol of sodium hydroxide and 20mL of toluene were mixed and reacted at 110℃for 12h. Then pouring 2M ammonium chloride aqueous solution and dichloromethane for extraction, drying and removing the organic solvent to obtain a crude product, and using a mixed solvent of petroleum ether and dichloromethane as a eluting agent and performing column chromatography purification to obtain a compound 4 (4, 4' - (dithieno [2,3-a:3',2' -c ] phenazine-2,5,9,10-tetrayl) tetra (N, N-diphenylaniline)).
The results of compound 4 nuclear magnetic resonance test are as follows:
1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.29(s,2H),7.84(s,2H),7.71(d,J＝8.4Hz,4H),7.31(m,14H),7.15(m,28H),7.04(m,10H)。
the thermal gravimetric analysis of compound 4 revealed a cleavage temperature of 467 ℃.
An electroluminescent red light device 4 was prepared according to the method of example 1, and its structure was: ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 4 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The change trend of the current density of the electroluminescent red light device 4 with the voltage was tested, and it was found that the compound 4 had semiconductor characteristics with a threshold voltage of 3.3V.
Testing the change trend of the brightness of the electroluminescent red light device 4 along with the change of voltage to obtain the maximum brightness of the device reaching 17866 cd.m -2 。
The change trend of the current efficiency of the electroluminescent red light device 4 along with the change of the brightness is tested, and the brightness of the device is 3.4 cd.m -2 When the current efficiency reaches the maximum value of 18.3 cd.A -1 。
Testing the change trend of the power efficiency of the electroluminescent red light device 4 along with the change of brightness to obtain the brightness of the device at 3.4 cd-m -2 When the power efficiency reaches the maximum value of 16.9 lm.W -1 。
Testing the change trend of the external quantum efficiency of the electroluminescent red light device 4 on the change of the current density to obtain the brightness of the device at 3.4 cd-m -2 When the maximum external quantum efficiency was 16.6%.
The electroluminescent spectrum of the electroluminescent red light device 4 is shown in FIG. 8, from which the electroluminescent peak of the device is seen at 616 nm.
Example 5
(1) 1mmol of 5, 6-dibromobenzo [ c ] [1,2,5] thiadiazole, 1mmol of triphenylamine-4-boronic acid pinacol ester, 0.05mmol of tetrakis (triphenylphosphine) palladium, 0.1mmol of tetrabutylammonium bromide, 6mmol of sodium hydroxide and 20ml of toluene were mixed and reacted at 110℃for 12h. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, removing an organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and petroleum ether (the volume ratio of the dichloromethane to the petroleum ether is 1:6) as a leaching agent to obtain 4- (6-bromobenzo [ c ] [1,2,5] thiadiazol-5-yl) -N, N-diphenyl aniline:
(2) 1mmol of 4- (6-bromobenzo [ c ] is taken][1,2,5]Thiadiazol-5-yl) -N, N-diphenyl aniline, 0.005mmol of palladium acetate, 2mmol of sodium acetate, 2mmol of diphenyl phosphine and 20mL of N, N-dimethylformamide are mixed, reacted for 12H at 135 ℃, and 5mmol of H is added 2 O 2 After the oxidation, adding water and dichloromethane for extraction, combining organic layers, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and methanol (the volume ratio of the dichloromethane to the methanol is 60:1) as a leaching agent to obtain (6- (4- (diphenylamino) phenyl) benzo [ c)][1,2,5]Thiadiazol-5-yl) diphenyl phosphine oxide:
(3) Mixing 0.05mmol of cobalt chloride hexahydrate, 7mmol of sodium borohydride and 10mL of methanol with 1mmol of the product obtained in the previous step, reacting at 80 ℃ for 48 hours, extracting with water and dichloromethane, combining organic layers, drying, and purifying by column chromatography with a mixed solvent of dichloromethane and ethyl acetate as a leaching agent to obtain an aromatic amine compound, namely a reactant II:
(4) 1mmol of benzodithiophene-4, 5-dione, 2mmol of reactant II and 20mL of acetic acid are taken and mixed, the mixture is reacted for 12h at 120 ℃, water and methylene chloride are used for extraction, the organic layers are combined, the mixture is dried, and a mixed solvent of methylene chloride and ethyl acetate (the volume ratio of the two is 8:1) is used as a leaching agent for column chromatography purification, so that the compound 5 ((10- (4- (diphenylamino) phenyl) dithiophene [2,3-a:3',2' -c ] phenazine-9-yl) diphenyl phosphine oxide) is obtained.
The results of compound 5 nmr test are as follows:
1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.35(d,J＝16.4Hz,1H),8.30(d,J＝4.4Hz,1H),7.88(dd,J＝13.6Hz,2H),7.80(dd,J 1 ＝2.4Hz,J 2 ＝5.2Hz,2H),7.74(dd,J 1 ＝7.2Hz,J 2 ＝11.6Hz,4H),7.58(d,J＝8.6Hz,2H),7.30(t,J＝7.9Hz,4H),7.21–7.13(m,6H),7.08(t,J＝7.3Hz,2H)。
the toluene solution of compound 5 and the film of compound 5 were tested for ultraviolet absorption spectrum and photoluminescence spectrum (fluorescence spectrum), as shown in fig. 3.
Compound 5 was subjected to thermogravimetric analysis and the cleavage temperature was 445 ℃ as seen in fig. 4.
An electroluminescent red light device 5 was prepared as in example 1: ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 5 (40%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm). .
The change trend of the current density of the electroluminescent red light device 5 with the voltage was tested, and it was found that the compound 5 had semiconductor characteristics with a threshold voltage of 4.4V.
The change trend of the brightness of the electroluminescent red light device 5 with the voltage was tested, and as shown in FIG. 13, the maximum brightness of the device could reach 7955 cd.m -2 。
The change trend of the current efficiency of the electroluminescent red light device 5 with the change of luminance was tested, as shown in FIG. 14, to obtain a luminance of the device at 2.7cd.m -2 When the current efficiency reaches the maximum value of 8.96 cd.A -1 。
The change trend of the power efficiency of the electroluminescent red light device 5 with the change of the luminance was tested, as shown in FIG. 15, to obtain a luminance of the device at 2.7cd.m -2 When the power efficiency reaches the maximum value of 5.21 lm.W -1 。
The change trend of the external quantum efficiency of the electroluminescent red light device 5 with respect to the change of luminance was tested, as shown in FIG. 16, to obtain a device having a luminance of 2.7 cd.m -2 When the most excellent is obtainedThe large external quantum efficiency is 8.0%.
The electroluminescent spectrum of the electroluminescent red light device 5 is shown in FIG. 9, from which it is seen that the electroluminescent peak of the device is at 632 nm.
Example 6
(1) Intermediate II was prepared as in the preparation of the compound of example 5. The only differences are: the benzodithiophene-4, 5-dione was replaced with an equimolar amount of 2, 7-dibromobenzodithiophene-4, 5-dione. Intermediate II:
(2) Mixing 1mmol of intermediate II, 0.005mmol of palladium acetate, 2mmol of sodium acetate, 2mmol of diphenylphosphine and 20mL of N, N-dimethylformamide, reacting at 135 ℃ for 12H, and adding 5mmol of H 2 O 2 And (5) oxidizing. After the reaction is finished, adding water and dichloromethane for extraction, combining the organic layers, drying, removing the organic solvent, and purifying by column chromatography with a mixed solvent of dichloromethane and methanol (the volume ratio of the dichloromethane to the methanol is 50:1) as a leaching agent to obtain a compound 6 ((10- (4- (diphenylamino) phenyl) dithioeno [2,3-a:3',2' -c) ]Phenazine-2, 5, 9-triyl) tris (diphenylphosphine oxide)).
The results of the compound 6 nuclear magnetic resonance test are as follows: 1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.28(s,1H),8.24(m,1H),8.17(d,J＝7.6Hz,1H),8.13(d,J＝7.6Hz,1H),7.83(m,8H),7.69(m,8H),7.53(m,10H),7.43(m,4H),7.33(d,J＝8.4Hz,2H),7.26(m,4H),7.03(m,6H),6.83(d,J＝8.4Hz,2H)。
the compound 6 was subjected to thermogravimetric analysis, and the cleavage temperature was found to be 426 ℃.
Device 6 was prepared as in example 5: ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 6 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The change trend of the current density of the electroluminescent red device 6 with the voltage was tested, and it was found that the compound 6 had semiconductor characteristics with a threshold voltage of 3.6V.
The change trend of the luminance of the electro-red light device 6 with the change of voltage was tested,the maximum brightness of the obtained device can reach 15467 cd.m -2 。
Testing the change trend of the current efficiency of the electroluminescent red light device 6 along with the change of brightness to obtain the brightness of the device at 2.77 cd.m -2 When the current efficiency reaches the maximum value of 15.7cd.A -1 。
Testing the change trend of the power efficiency of the electroluminescent red light device 6 along with the change of brightness to obtain the brightness of the device at 2.77 cd.m -2 When the power efficiency reaches the maximum value of 14.4 lm.W -1 。
Testing the change trend of the external quantum efficiency of the electroluminescent red light device 6 to the change of the current density to obtain the brightness of the device at 2.77 cd.m -2 When the maximum external quantum efficiency was 19.2%.
The electroluminescent spectrum of the electroluminescent red light device 6 is shown in FIG. 10, from which the electroluminescent peak of the device is seen at 648 nm.
Example 7
(1) Intermediate ii was prepared according to the procedure in example 6.
(2) 1mmol of intermediate II, 5mmol of cuprous cyanide and 20ml of N, N-dimethylformamide are mixed and reacted at 140℃for 12h. Then pouring mixed solution of ferric trichloride and hydrochloric acid and dichloromethane for extraction, drying and removing the organic solvent to obtain a crude product, taking the mixed solvent of dichloromethane and ethyl acetate (the volume ratio of the dichloromethane to the ethyl acetate is 6:1) as a leaching agent, and performing column chromatography purification to obtain a compound 7 (9- (4- (diphenylamino) phenyl) -10- (diphenylphosphoryl) dithieno [2,3-a:3',2' -c ] phenazine-2, 5-dimethylnitrile).
The results of the compound 7 nuclear magnetic resonance test are as follows:
1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.26(m,4H),7.72(dd,J 1 ＝7.6Hz,J 2 ＝12Hz,4H),7.56(t,J＝7.2Hz,2H),7.47(m,4H),7.39(d,J＝8Hz,2H),7.26(m,4H),7.04(dd,J 1 ＝7.6Hz,J 2 ＝12Hz,6H),6.87(d,J＝8Hz,2H).
the resulting compound 7 was subjected to thermogravimetric analysis, and the cleavage temperature of the resulting compound was 420 ℃.
According to embodiment 1 of the electroluminescent red light device 1The preparation method comprises the steps of preparing an electroluminescent red light device 7 by taking a mixture of a compound 7 and CBP (wherein the mass fraction of the compound 7 is 20%) as a luminescent layer material, wherein the electroluminescent red light device has the structure of ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 7 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The change trend of the current density of the electroluminescent red device 7 with voltage was tested, and it was found that the compound 7 had semiconductor characteristics with a threshold voltage of 3.1V.
Testing the change trend of the brightness of the electroluminescent red light device 7 along with the change of voltage to obtain the maximum brightness of the device up to 14473 cd-m -2 。
Testing the change trend of the current efficiency of the electroluminescent red light device 7 along with the change of brightness to obtain the brightness of the device at 3.2 cd.m -2 When the current efficiency reaches the maximum value of 15.3 cd.A -1 。
Testing the change trend of the power efficiency of the electroluminescent red light device 7 along with the change of brightness to obtain the brightness of the device at 3.2 cd.m -2 When the power efficiency reaches the maximum value of 15.7lm.W -1 。
Testing the change trend of the external quantum efficiency of the electroluminescent red light device 7 to the change of the current density to obtain the brightness of the device at 3.2 cd.m -2 When the maximum external quantum efficiency was 23.7%.
The electroluminescent spectrum of the electroluminescent red light device 7 is shown in FIG. 11, from which it can be seen that the electroluminescent peak of the device is at 660 nm.
Example 8
(1) Intermediate ii synthesized according to example 6.
(2) 1mmol of intermediate II, 2mmol of triphenylamine-4-boric acid, 0.025mmol of tetrakis (triphenylphosphine) palladium, 0.2mmol of tetrabutylammonium bromide, 6mmol of sodium hydroxide and 20mL of toluene were mixed and reacted at 110℃for 12h. Then pouring 2M ammonium chloride aqueous solution and dichloromethane for extraction, drying and removing the organic solvent to obtain a crude product, and taking a mixed solvent of dichloromethane and methanol (the volume ratio of the dichloromethane to the methanol is 20:1) as a leaching agent and performing column chromatography purification to obtain a compound 8 (diphenyl (2, 5, 10-tris (4- (diphenylamino) phenyl) dithieno [2,3-a:3',2' -c ] phenazin-9-yl) phosphine oxide).
The obtained compound 8 is subjected to nuclear magnetic resonance hydrogen spectrum analysis, and the test data are as follows: 1 H NMR(TMS,CDCl 3 ,400MHz):δ＝8.28(d,J＝21.6Hz,2H),8.22(d,J＝5.2Hz,2H),7.82(t,J＝2.4Hz,2H),7.70(m,8H),7.51(m,2H),7.43(m,4H),7.31(m,12H),7.09(m,24H),6.94(d,J＝11.6Hz,2H).
the resulting compound 8 was subjected to thermogravimetric analysis, and the cleavage temperature of the resulting compound was 433 ℃.
According to the method for manufacturing an electroluminescent red light device in example 1, an electroluminescent red light device 8 having a structure of ITO/MoO was manufactured using a mixture of compound 8 and CBP (wherein the mass fraction of compound 8 is 20%) as a light emitting layer material 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 8 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The change trend of the current density of the electroluminescent red device 8 with the voltage was tested, and it was found that the compound 8 had semiconductor characteristics with a threshold voltage of 3.2V.
Testing the change trend of the brightness of the electroluminescent red light device 8 along with the change of voltage to obtain the maximum brightness of the device reaching 10354 cd.m -2 。
The change trend of the current efficiency of the electroluminescent red light device 8 along with the change of the brightness is tested, and the brightness of the device is 3.4 cd.m -2 When the current efficiency reaches the maximum value of 11.3 cd.A -1 。
Testing the change trend of the power efficiency of the electroluminescent red light device 8 along with the change of brightness to obtain the device with the brightness of 3.4 cd.m -2 When the power efficiency reaches the maximum value of 12.5 lm.W -1 。
Testing the change trend of the external quantum efficiency of the electroluminescent red light device 8 on the change of the current density to obtain the brightness of the device at 3.4 cd-m -2 When the maximum external quantum efficiency was 20.2%.
The electroluminescent spectrum of the electroluminescent red light device 8 is shown in FIG. 12, from which the electroluminescent peak of the device is seen at 640 nm.
The present invention has been described in detail in connection with the detailed description and/or the exemplary examples and the accompanying drawings, but the description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (6)
1. A dithienophenazine receptor-based compound, characterized in that the dithienophenazine receptor-based compound is selected from one of compounds 1 to 8, and compounds 1 to 8 are specifically as follows:
2. a process for the preparation of a dithienophenazine receptor based compound according to claim 1, characterized in that it comprises the following steps:
step 1, preparing an o-aminobenzene compound by using 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole, wherein the o-aminobenzene compound is 4- (4-diphenylamino) phenyl-5-diphenylphosphinyloxy o-phenylenediamine or 4, 5-bis (4-diphenylamino) phenyl-o-phenylenediamine;
Step 2, carrying out ring closure reaction on an o-aminobenzene compound and a benzodithiophene-4, 5-dione compound to obtain an intermediate, wherein the benzodithiophene-4, 5-dione compound is benzodithiophene-4, 5-dione or 2, 7-dihalogenated benzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione, and the halogenation is bromination, iodination or chlorination;
and 3, reacting the intermediate with an aromatic amine compound, an aromatic phosphine compound or a cyano compound to obtain a compound based on a dithienophenazine receptor.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
in the step 1, the 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole is reacted with an aromatic amine boron compound to obtain 4,4' - (benzo [ c ] [1,2,5] thiadiazole-5, 6-diyl) bis (N, N-diphenyl aniline) or 4- (6-bromobenzo [ c ] [1,2,5] thiadiazole-5-yl) -N, N-diphenyl aniline;
the 5,6- (4-diphenylamino) phenyl benzo [ c ] [1,2,5] thiadiazole is reduced to obtain 4,5- (4-diphenylamino) phenyl o-phenylenediamine;
the 4- (6-bromobenzo [ c ] [1,2,5] thiadiazole-5-yl) -N, N-diphenyl aniline reacts with diphenyl phosphine, and is oxidized by hydrogen peroxide to obtain (6- (4- (diphenyl amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-5-yl) diphenyl phosphine oxide, and then is reduced to obtain 4-4- (diphenyl amino) phenyl-5-diphenyl phosphinyloxy o-phenylenediamine.
4. The method according to claim 2, wherein, in step 2,
the benzodithiophene-4, 5-dione compound is benzodithiophene-4, 5-dione, the o-aminobenzene compound is 4- (4-diphenylamino) phenyl-5-diphenylphosphinyloxy o-phenylenediamine or 4, 5-di (4-diphenylamino) phenyl-o-phenylenediamine, and the compound 1 or the compound 5 is obtained through reaction;
the benzodithiophene-4, 5-diketone compound is 2, 7-dihalogenated benzo [1,2-B:6,5-B' ] dithiophene-4, 5-diketone, the o-aminobenzene compound is 4- (4-diphenylamino) phenyl-5-diphenylphosphinyloxy o-phenylenediamine or 4, 5-bis (4-diphenylamino) phenyl-o-phenylenediamine, the intermediate is obtained by reaction,
the intermediate is as follows:
wherein X is 0 Is chlorine, iodine or bromine; x is X 1 、X 2 Are each diphenylaminophenyl or X 1 Is diphenyl aminophenyl, X 2 Is diphenylphosphinyloxy.
5. The method according to claim 2, wherein, in step 3,
the aromatic amine compound is triphenylamine-4-boric acid pinacol ester or triphenylamine-4-boric acid, and a compound 4 and a compound 8 are obtained;
the aromatic phosphine oxide compound is diphenyl phosphine, and compound 2 and compound 6 are obtained;
the cyano compound is cuprous cyanide, and compound 3 and compound 7 are obtained.
6. Use of a dithiophene-based compound according to claim 1 as a light emitting layer material for the preparation of an electroluminescent device having a luminance of 7500-26000 cd-m -2 The external quantum efficiency is 5% -24%, and the electroluminescent wavelength is 580-660nm.
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| CN110028506A (en) * | 2019-04-30 | 2019-07-19 | 黑龙江大学 | The red orange photo-thermal excitation delayed fluorescence material of two pyrido phenazinyl, synthetic method and its application |
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| KR20170106802A (en) * | 2016-03-14 | 2017-09-22 | 건국대학교 산학협력단 | Phenazine derivatives with the extended conjugated structure and applied to the organic photovoltaic polymers |
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