CN115710280A - Compound based on dithienophenazine receptor, synthetic method and application thereof - Google Patents
Compound based on dithienophenazine receptor, synthetic method and application thereof Download PDFInfo
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- CN115710280A CN115710280A CN202211378894.9A CN202211378894A CN115710280A CN 115710280 A CN115710280 A CN 115710280A CN 202211378894 A CN202211378894 A CN 202211378894A CN 115710280 A CN115710280 A CN 115710280A
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- Prior art keywords
- compound
- aromatic
- nitrogen
- receptor
- containing aryl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 102
- 238000010189 synthetic method Methods 0.000 title description 4
- 108010031480 Artificial Receptors Proteins 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 61
- 125000003118 aryl group Chemical group 0.000 claims abstract description 41
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 14
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- -1 aminophenyl Chemical class 0.000 claims description 109
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 18
- 229940125904 compound 1 Drugs 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229940125898 compound 5 Drugs 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- TWWQCBRELPOMER-UHFFFAOYSA-N [4-(n-phenylanilino)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 TWWQCBRELPOMER-UHFFFAOYSA-N 0.000 claims description 10
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- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 7
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- 229940125782 compound 2 Drugs 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 6
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- MKPDAJWEBQRQCO-UHFFFAOYSA-N (4-aminophenyl)boronic acid Chemical class NC1=CC=C(B(O)O)C=C1 MKPDAJWEBQRQCO-UHFFFAOYSA-N 0.000 claims description 3
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- 239000012312 sodium hydride Substances 0.000 claims description 2
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a compound based on a dithienophenoxazine receptor, which takes the dithienophenoxazine receptor as a parent and contains one or more substituents of nitrogen-containing aryl, aromatic phosphine oxide groups and cyano groups as a donor. The red light thermal excitation delayed fluorescence material can improve the transmission capability of current carriers, weaken quenching effect, block conjugate extension and ensure the emission wavelength of the material, thereby obtaining the red light thermal excitation delayed fluorescence material with stable thermal property and electrical property.
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 synthetic method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) have the advantages of low driving voltage, fast response, wide viewing angle, ultra-thin, flexible display, and the like, and have been widely used for display screens of smart phones, watches, computers, and other devices. The first generation of organic electroluminescent materials are fluorescent materials, which only use singlet excitons to emit light, so that theoretically the internal quantum efficiency can only reach 25%. The second generation electroluminescent material is a phosphorescent material based on a heavy metal complex, and can realize 100% internal quantum efficiency by simultaneously utilizing singlet exciton luminescence and triplet exciton luminescence; however, the expensive cost of the metal complex and environmental pollution remain unsolved problems.
The advent of third generation Thermally Activated Delayed Fluorescence (TADF) materials has provided researchers with new design ideas. The TADF material is characterized in that triplet excitons can be converted into radiation-transitable singlet excitons through reverse intersystem crossing under the heat assistance, thereby realizing light emission by simultaneously utilizing singlet and triplet excitons and realizing 100% internal quantum efficiency.
Most TADF light-emitting molecules are of a pure organic Donor (Donor) -Acceptor (Acceptor) structure. Smaller singlet-triplet energy differences (. DELTA.E) achieved by using distorted donor (D) and acceptor (A) configurations ST ) And TADF characteristics, since well separated Highest Occupied Molecular Orbital (HOMO) and lowest unoccupied molecular orbital (HOMO) can minimize Δ E ST . Rapid reverse intersystem crossing (RISC) is achieved, thereby utilizing triplet excitons to emit light and reducing quenching of the triplet excitons. Compared with fluorescence and phosphorescence technologies, TADF materials have the advantages of resource sustainability, low cost, and environmental friendliness. However, efficient singlet irradiation requires sufficient overlap of the initial and final states. Therefore, a small Δ E ST And high photoluminescence quantum yield (PLQY) are one of the key contradictions for constructing highly efficient TADF materials.
The luminous efficiency of red TADF molecules is extremely sensitive to the doping concentration, leading to an efficiency loss of even up to 80% with undoped light-emitting layer structures. In addition to the greater polarity of the molecule itself, there is a more severe process of nonradiative transition on its own. Currently, few undoped red TADF devices can have an External Quantum Efficiency (EQE) of over 10%. Therefore, the photoelectric property of the red TADF molecule itself is a key bottleneck for restricting the performance improvement of the undoped red TADF device.
Four strategies are provided for improving the Photoluminescence (PL) and Electroluminescence (EL) performance of red TADF emitters: (1) Reasonable molecular accumulation and intermolecular interaction are realized to realize both charge transmission and quenching inhibition; (2) The radiative process has absolute advantages over the non-radiative process to obtain high luminous efficiency; (3) The RISC efficiency approaches 100% to gain the thermodynamic advantage of delayed fluorescence; (4) Rapid charge recombination and exciton irradiation to avoid quenching by exciton accumulation.
In order to realize a red TADF material, it is usually necessary to further enhance the interaction between the donor and acceptor, and a stronger interaction tends to increase the polarity of the material, and the intermolecular interaction is enhanced, resulting in severe concentration quenching. Therefore, how to obtain a high-efficiency red TADF material, it is a difficult scientific problem to develop a luminescent material satisfying the above requirements.
Disclosure of Invention
To solve the above problems, the present invention provides a compound containing a dithienophenazine receptor. The compound takes dithiophene phenazine as an acceptor, and modifies nitrogen-containing aryl, aromatic phosphine oxide groups and cyano groups as donors, so that the transmission capability of current carriers is improved, the quenching effect is weakened, the conjugate extension is blocked, and the emission wavelength of the material is ensured, thereby obtaining the red light thermal excitation delay fluorescent material with stable thermal property and electrical property, and completing the invention.
The object of the first aspect of the present invention is to provide a compound based on a dithienophenoxazine receptor, wherein the dithienophenoxazine receptor is used as a precursor and one or more substituents selected from nitrogen-containing aryl groups, aromatic phosphino-oxy groups and cyano groups are used as donors.
The second aspect of the invention also provides a method for preparing the compound based on the dithiophene phenazine receptor. According to the method, 5, 6-dihalogenobenzo [ c ] [1,2,5] thiadiazole is used as an initial material to prepare an o-aminobenzene compound, then the o-aminobenzene compound and benzodithiophene-4, 5-diketone compound are subjected to ring closure, and a nitrogen-containing aryl group, an aromatic phosphine oxide group or a cyano group are grafted to obtain a compound based on a dithiophene phenazine receptor.
The o-aminobenzene compound has the following structure:
wherein, X 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphine oxide groups, preferably from diphenylaminophenyl or diphenylphosphinyloxy.
The benzodithiophene-4, 5-diketone compound is benzodithiophene-4, 5-diketone or 2, 7-dibromobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-diketone.
The method comprises the following steps:
and 3, reacting the intermediate with an aromatic amine compound, an aromatic phosphine compound or a cyano compound to obtain the compound based on the dithiophene phenazine receptor.
The third aspect of the invention aims to provide the application of the compound based on the dithienophenazine receptor as a luminescent layer material for preparing an electroluminescent red device.
The fourth aspect of the invention aims to provide an electroluminescent device, and the material of a light-emitting layer of the electroluminescent device comprises the compound based on the dithiophene phenazine receptor.
The invention has the following beneficial effects:
(1) The compound based on the dithieno-phenazine acceptor is used as a red light thermal excitation delay fluorescent material, the introduced aromatic amine group is a strong electron-donating group, the transmission capability of a current carrier can be improved, a reasonable molecular accumulation state and intermolecular acting force can be obtained by utilizing the steric effect of the aromatic phosphine-oxygen group, and meanwhile, the phosphine-oxygen group is utilized to block conjugation extension, so that the quenching effect is weakened.
(2) The diphenylphosphine oxide group has proper electron-withdrawing ability, strong steric hindrance effect and hydrogen bond ability, can effectively red shift wavelength and reduce delta E ST Concentration quenching is suppressed, and TADF efficiency is improved.
(3) The invention has reasonable molecular accumulation and intermolecular interaction to ensure electron transmission and inhibit concentration quenching by designing a molecular structure, thereby obtaining the red TADF material.
(4) The maximum external quantum efficiency of the prepared electroluminescent red light device can reach 23.7 percent at most, and meanwhile, the luminescent 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 thermogravimetric analysis spectrum 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 thermogravimetric analysis spectrum of Compound 5 in example 5 of the present invention;
FIG. 5 shows a diagram of the electroluminescence spectrum of the electroluminescent red device 1 in example 1 of the present invention;
FIG. 6 shows a diagram of the electroluminescence spectrum of an electroluminescent red device 2 in example 2 of the present invention;
FIG. 7 shows a diagram of the electroluminescence spectrum of an electroluminescent red device 3 in example 3 of the present invention;
FIG. 8 shows a graph of the electroluminescence spectrum of the electroluminescent red device 4 in example 4 of the present invention;
FIG. 9 shows a diagram of the electroluminescence spectrum of an electroluminescent red device 5 in example 5 of the present invention;
FIG. 10 shows a diagram of the electroluminescence spectrum of an electroluminescent red device 6 in example 6 of the present invention;
FIG. 11 shows an electroluminescence spectrum of an electroluminescent red device 7 in example 7 of the present invention;
FIG. 12 shows a graph of the electroluminescence spectrum of an electroluminescent red device 8 in example 8 of the present invention;
FIG. 13 shows the voltage-luminance relationship of the electroluminescent device 5 in example 5 of the present invention;
FIG. 14 shows the luminance-current efficiency relationship of the electroluminescent device 5 in example 5 of the present invention;
FIG. 15 shows the luminance-power efficiency relationship of the electroluminescent device 5 in example 5 of the present invention;
fig. 16 shows the luminance-external quantum efficiency relationship curve of the electroluminescent device 5 in example 5 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments, and features and advantages of the present invention will become more apparent and apparent with reference to the description.
The compound based on the dithienophene phenazine receptor provided by the invention takes dithieno phenazine as the receptor, and modifies nitrogen-containing aryl, aromatic phosphine oxide group and cyano group as the donor, so as to obtain the red light thermal excitation delay fluorescent material. Compared with the existing thermal excitation delay fluorescent material, the compound has the advantages that the carrier transmission capability is improved, the quenching effect is further weakened, the aromatic phosphine oxide group can block the conjugated extension, the emission wavelength of the material is ensured, and the electroluminescent device obtained by the compound has good red light luminous performance.
The invention provides a compound based on a dithiophene phenazine receptor, wherein the dithiophene phenazine receptor is used as a parent body, and one or more substituents of a nitrogen-containing aryl group, an aromatic phosphine oxide group and a cyano group are used as donors.
The compounds have the general formula:
wherein X 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinoxy groups, preferably aryl-substituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably from diphenylaminophenyl or diphenylphosphinoxy.
R 1 、R 2 Each independently selected from hydrogen, cyano, nitrogen-containing aryl or aromatic phosphinoxy groups, preferably hydrogen, cyano, aryl-substituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably hydrogen, cyano, diphenylaminophenyl or diphenylphosphinoxy.
Preferably, the compound based on a dithiophene phenazine receptor is selected from one of the compounds 1 to 8, and the compounds 1 to 8 are specifically as follows:
the compound based on the dithienophenoxazine receptor provided by the invention is used as a dithienophenoxazine red-light thermal excitation delay fluorescent material, and the introduced nitrogen-containing aryl, such as triphenylamine group, is a strong electron-donating group, so that the transmission capability of a carrier can be improved, and the Intramolecular Charge Transfer (ICT) capability and RISC efficiency can be improved. The cyano group has strong electron-withdrawing ability, and the introduction of the group can enable the spectrum of the compound of the system to obtain obvious red shift. The steric effect of the aromatic phosphine-oxygen group can obtain reasonable molecular accumulation state and intermolecular acting force, so that the quenching effect is weakened, the photoluminescence quantum yield of the material serving as a thermal excitation delayed fluorescence luminescent material is improved, the luminescent efficiency of a device is improved, and the emission wavelength of the material is ensured.
In addition, the aromatic phosphine oxide group has proper electron-withdrawing ability and stronger steric hindrance effectAnd hydrogen bond forming ability, effective red shift of wavelength, and reduction of Δ E ST Concentration quenching is suppressed, and TADF efficiency is improved. Therefore, the introduction of phosphine-oxygen group into the donor-acceptor structure can adjust the molecular configuration, the electrical property and the like of the material, so as to realize the high-efficiency red TADF material.
In addition, the compound based on the dithiophene phenazine receptor provided by the invention also has good thermal stability, so that the stability of the device is improved. The electroluminescent device is used as a guest material of a luminescent layer, and the current efficiency and the power efficiency of the electroluminescent device are effectively improved.
In view of the numerous advantages of the dithienophenoxazine acceptor, which improves the charge transport capability of the material and the above-mentioned diphenylphosphine oxide group, compounds 1-4 are preferred, which have higher brightness and external quantum efficiency than the current common TADF red light molecule. With the increase of the number of diphenyl phosphorus oxygen groups in the compound based on the dithiophene phenazine receptor, preferably the compounds 5-8, the emission wavelength can be red shifted, and simultaneously higher electroluminescent performance can be obtained.
The second aspect of the invention also provides a method for preparing the compound based on the dithiophene phenazine receptor. The method takes 5, 6-dihalogenobenzo [ c ] [1,2,5] thiadiazole as an initial material to prepare an o-aminobenzene compound, and then the o-aminobenzene compound is cyclized with a benzodithiophene-4, 5-diketone compound to obtain a compound based on a dithienophenazine receptor; or 5, 6-dihalogenobenzo [ c ] [1,2,5] thiadiazole is used as an initial material to prepare an o-aminobenzene compound, then the o-aminobenzene compound and benzodithiophene-4, 5-diketone compound are subjected to ring closure, and a nitrogen-containing aryl group, an aromatic phosphine oxide group or a cyano group are grafted to obtain the compound based on the dithiophene phenazine receptor.
The o-aminobenzene compound has the following structure:
wherein, X 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphine oxide groups, preferably from arylSubstituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably diphenylaminophenyl or diphenylphosphinoxy.
Preferably, the o-aminobenzene compound is 4-nitrogen-containing aryl-5-aromatic phosphinoxy o-phenylenediamine or 4, 5-bis-nitrogen-containing aryl o-phenylenediamine, wherein the nitrogen-containing aryl is preferably aryl-substituted aminophenyl, and the aromatic phosphinoxy is preferably phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, and more preferably, the o-aminobenzene compound is 4- (4-diphenylamino) phenyl-5-diphenylphosphinoxy o-phenylenediamine or 4, 5-bis (4-diphenylamino) phenyl-o-phenylenediamine.
The benzodithiophene-4, 5-dione compound is benzodithiophene-4, 5-dione or 2, 7-dihalobenzo [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:
In the 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole, the halogenation is bromination, iodo or chlorination, and the bromination is preferred.
The 5, 6-dihalogenobenzo [ c ] [1,2,5] thiadiazole reacts 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-halobenzo [ c ] [1,2,5] thiadiazole.
The reaction with aromatic amine boron compound is carried out for 10-14h at 100-120 ℃ under the alkaline condition and in the presence of palladium catalyst and solvent. 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.
The 5, 6-dinitrogen-containing aryl benzo [ c ] [1,2,5] thiadiazole is reduced to obtain 4, 5-dinitrogen-containing aryl o-phenylenediamine. Preferably, the reduction is carried out by sodium borohydride in the presence of a solvent and a 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, and more preferably methanol.
The 5-nitrogen-containing aryl-6-halogenobenzo [ c ] [1,2,5] thiadiazole reacts with an aromatic phosphine compound, the 5-nitrogen-containing aryl-6-aromatic phosphinyloxybenzo [ c ] [1,2,5] thiadiazole is obtained through oxidation and oxidation of hydrogen, and then the 4-nitrogen-containing aryl-5-aromatic phosphinyloxy o-phenylenediamine is obtained through reduction.
The 5-nitrogen-containing aryl-6-halogenobenzo [ c ] [1,2,5] thiadiazole reacts with an aromatic phosphine compound, and the reaction is carried out for 10 to 14 hours at 125 to 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, and 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 lasts 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, and more preferably methanol.
The aromatic amine boron compound is selected from aryl substituted aminobenzene-4-boronic acid pinacol ester or aryl substituted aminobenzene-4-boronic acid, preferably triphenylamine-4-boronic acid pinacol ester or triphenylamine-4-boronic acid, and more preferably triphenylamine-4-boronic 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 phenyl phosphine, diphenyl phosphine or triphenyl phosphine, and is preferably diphenyl phosphine. The aromatic phosphinoxy group is selected from phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, preferably diphenylphosphinoxy.
And 2, performing a 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, and the o-aminobenzene compound is 4, 5-dinitrogen-containing aryl o-phenylenediamine or 4-dinitrogen-containing aryl-5-aromatic phosphinyl o-phenylenediamine, and the compound 1 or the compound 5 is obtained through reaction.
In another embodiment of the present invention, the benzodithiophene-4, 5-dione compound is 2, 7-dihalobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione, and the o-aminobenzene compound is 4, 5-dinitrogen-containing aryl o-phenylenediamine or 4-dinitrogen-containing aryl-5-aromatic phosphinoxy o-phenylenediamine, and the reaction gives an intermediate.
The intermediate is as follows:
wherein, X 0 Is chlorine, iodine or bromine, preferably bromine; x 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinoxy groups, preferably aryl-substituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphinoxy, more preferably diphenylaminophenyl or diphenylphosphinoxy. More preferably, X 1 、X 2 Are both diphenylaminophenyl or X 1 Is diphenylaminophenyl, 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, and preferably acetic acid. The mol ratio of the o-aminobenzene compound to the benzodithiophene-4, 5-diketone compound is (1.0-2.0): 1, preferably (1.2-1.5): 1, and more preferably 1.5).
And 3, reacting the intermediate with an aromatic amine compound, an aromatic phosphine compound or a cyano compound to obtain a compound based on the dithiophene phenazine receptor.
The aromatic amine compound is selected from aryl-substituted aminobenzene-4-boronic acid pinacol ester or aryl-substituted aminobenzene-4-boronic acid, and is preferably triphenylamine-4-boronic acid pinacol ester or triphenylamine-4-boronic acid. The intermediate reacts with the aromatic amine compound to yield a compound based on the dithiophene phenazine receptor, and at this time,
in, R 1 、R 2 All of which are nitrogen-containing aryl groups, preferably amino aryl groups, more preferably diphenylamino phenyl groups, such as compound 4, compound 8.
The intermediate reacts with aromatic amine boron compound under alkaline condition and in the presence of palladium catalyst and solvent at 100-120 ℃ for 10-14h. The solvent is one or more of aromatic hydrocarbon solvents, preferably toluene and/or xylene, and more preferably toluene.
The aromatic phosphine compound is phenyl phosphine, diphenyl phosphine or triphenyl phosphine, and diphenyl phosphine is preferred. The intermediate reacts with the aromatic phosphine compound, and the compound based on the dithiophene phenazine receptor is obtained through oxidation and oxidation of hydrogen,
in, R 1 、R 2 Both are aromatic phosphinoxy groups, preferably phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably diphenylphosphinoxy, such as compound 2, compound 6.
The intermediate reacts with an aromatic phosphine compound, the reaction is carried out for 10-14h at 125-145 ℃ in the presence of a palladium catalyst and a solvent, hydrogen peroxide is added after the reaction is finished, and post-treatment is carried out, so as to obtain the compound based on the dithiophene phenazine receptor. The solvent is selected from one or more of amide solvents, preferably N, N-dimethylformamide and/or N, N-dimethylacetamide, and 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, and more preferably cuprous cyanide. The intermediate is reacted with a cyano compound to give a compound based on a dithienophenazine receptor, in which case,
in, R 1 、R 2 Both cyano groups, such as compound 3, compound 7.
The intermediate reacts 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, and more preferably N, N-dimethylformamide.
The synthetic route of the compound based on the dithiophene phenazine receptor is reasonable in design, the synthetic method is easy to carry out, and the target product can be stably obtained.
The third aspect of the invention provides the application of the compound based on the dithienophenoxazine receptor of the first aspect as a luminescent layer material for preparing an electroluminescent red device.
The brightness of the electroluminescent red light device is 7500-26000 cd.m -2 Preferably 15000 to 25000 cd.m -2 More preferably from 16000 to 19000 cd.m -2 。
The external quantum efficiency of the electroluminescent red device is 5-24%, preferably 16-19%.
The electroluminescent wavelength of the electroluminescent red device is 580-660nm, preferably 600-650nm, more preferably 630-640nm.
In a fourth aspect, the invention provides an electroluminescent device, wherein the material of the light-emitting layer of the electroluminescent device comprises the dithienophenazine receptor-based compound, preferably the compound 1 to the compound 8, and more preferably the compound 5 to the compound 8.
The electroluminescent red device also 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 luminescent device taking the compound based on the dithiophene phenazine receptor as a luminescent 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, semi-transparent metals such as Au, preferably ITO or semi-transparent metals, more preferably ITO. Preferably, the conductive anode layer is evaporated by vacuum evaporation.
Preferably, vacuum evaporation vacuumIs 1 × 10 -6 mbar, setting the evaporation rate to 0.1-0.3 nm/s, and 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, 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 evaporated onto 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 evaporated onto the hole injection layer to a thickness of 25-75nm, preferably 35-65nm, more preferably 45-55nm, 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) and 9,9' - (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 evaporation thickness is 2-10nm, preferably 3-7nm, and more preferably 5nm;
the hole barrier layer material is 4,4' -tris (carbazol-9-yl) triphenylamine (TCTA) or 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), and preferably TCTA.
5. Preparing a luminescent layer;
the light-emitting layer is further evaporated on the hole-blocking layer to a thickness of 9-45nm, preferably 12-35nm, more preferably 15-25nm, such as 20nm.
The luminescent layer material comprises a compound based on a dithiophene phenazine acceptor, preferably also 4,4' -bis (9-Carbazole) Biphenyl (CBP), and the mass fraction of the compound based on a dithiophene phenazine acceptor 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 deposited on the light emitting layer to a thickness of 45 to 75nm, preferably 55 to 65nm, and 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 evaporated on the electron transport layer to a thickness of 1 to 15nm, preferably 1 to 10nm, more preferably 1 to 5nm, such as 1nm.
The material of the electron injection layer is selected from lithium tetrakis (8-hydroxyquinoline) boron (LiBq) 4 ) Or LiF, preferably LiF.
8. And preparing a cathode conducting layer, and packaging to obtain the thermal excitation delay fluorescence electroluminescent device.
The cathode conductive layer is evaporated on the electron injection layer to a thickness of 60 to 130nm, preferably 70 to 120nm, more preferably 80 to 110nm, such as 100nm.
The cathode conducting layer material is selected from a single metal cathode or an alloy cathode, such as metal 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 12 hours. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, removing the organic solvent, and performing column chromatography purification by using a mixed solvent of dichloromethane and petroleum ether (the volume ratio of the two is 1:
(2) 0.05mmmol of cobalt chloride hexahydrate, 7mmol of sodium borohydride and 10ml of methanol are taken to be respectively mixed with 1mmol of 4,4' - (benzo [ c ] [1,2,5] thiadiazole-5, 6-diyl) bis (N, N-diphenylaniline) obtained in the previous step, and the mixture reacts for 48 hours at 80 ℃. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, and performing column chromatography purification by using a mixed solvent of dichloromethane and ethyl acetate (the volume ratio of the two is 10:
(3) 1mmol of benzodithiophene-4, 5-dione, 2mmol of reactant I and 20mL of acetic acid are mixed and reacted at 120 ℃ for 12h. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, and performing column chromatography purification by using a mixed solvent of dichloromethane and petroleum ether (the volume ratio of the two is 1).
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 ultraviolet absorption spectrum and photoluminescence spectrum (fluorescence spectrum) of the toluene solution of compound 1 and the thin film of compound 1 were measured, as shown in fig. 1.
The thermogravimetric analysis of the obtained compound 1 was carried out, and as shown in FIG. 2, the cleavage temperature of the compound 1 was determined to be 486 ℃.
(3) And (3) preparing an electroluminescent red device by taking the obtained mixture of the compound 1 and CBP (wherein the mass fraction of the compound 1 is 20%) as a light-emitting layer guest material:
1. putting the glass substrate cleaned by the deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10 -6 mbar, evaporation rate set at 0.1nm s -1 The evaporation material is Indium Tin Oxide (ITO) to obtain an anode conducting layer with the thickness of 6 nm;
2. evaporating hole injection layer material MoO on the 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 5nm;
5. a light-emitting layer is vapor-plated on the hole blocking layer, and the material is a mixture of a compound 1 and CBP, wherein the mass fraction of the compound 1 is 20%, and the light-emitting layer with the thickness of 20nm is obtained;
6. continuously 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 and plating an electron injection layer material LiF on the electron transport layer to obtain an electron injection layer with the thickness of 1 nm;
8. and evaporating aluminum on the electron injection layer to form a cathode conducting layer with the thickness of 100nm to obtain the electroluminescent device 1.
The structure of the electroluminescent red 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).
By testing the variation trend of the current density of the electroluminescent device 1 with the voltage, the compound 1 is known to have semiconductor characteristics, and the threshold voltage thereof is 4.2V.
The variation trend of the brightness of the electroluminescent red light device 1 along with the voltage change is tested, and the maximum brightness of the device can reach 24461 cd.m -2 。
The current efficiency of the electroluminescent red device 1 is tested to change with the change of the brightness, and the brightness of the device is 2.3 cd.m -2 When the current efficiency reaches the maximum value of 14.5 cd.A -1 。
Testing the variation trend of the power efficiency of the electroluminescent red light device 1 along with the change of the brightness to obtain the brightness of the device of 2.3 cd.m -2 When the power efficiency reaches the maximum value of 10.8 lm.W -1 。
The variation trend of the external quantum efficiency of the electroluminescent red device 1 to the change of the current density is tested to obtain the brightness of the device of 3.0 cd.m -2 Then, a maximum external quantum efficiency of 5.58% was obtained.
The electroluminescence spectrum of the electroluminescent red device 1 is shown in FIG. 5, from which it can be seen that the electroluminescence peak of the device is at 588 nm.
Example 2
(1) Reactant I was prepared according to the procedure in example 1.
(2) 1mmol of 2, 7-dibromobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione, 2mmol of reactant I and 20ml of acetic acid are mixed and reacted at 120 ℃ for 12h. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, and performing column chromatography purification by using a mixed solvent of dichloromethane and ethyl acetate (the volume ratio of the two is 8.
(3) Mixing 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, reacting at 135 ℃ for 12H, and adding 5mmol of H 2 O 2 And (2) oxidizing, after the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, removing the organic solvent, and performing column chromatography purification by using a mixed solvent of dichloromethane and methanol (the volume ratio of the two is 50]Phenazine-2, 5-diyl) bis (diphenylphosphine oxide)).
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)。
thermogravimetric analysis of Compound 2 revealed that the cleavage temperature was 462 ℃.
An electroluminescent device 2 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 2 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The current density of the electroluminescent device 2 is tested to change along with the change of the voltage, and the compound 2 is known to have semiconductor characteristics, and the threshold voltage of the compound is 3.70V.
The variation trend of the brightness of the electroluminescent red device 2 along with the voltage change is tested, and the maximum brightness of the device can reach 18660 cd.m -2 。
The current efficiency of the electroluminescent red device 2 is tested to obtain the brightness of the device 2.54 cd.m -2 When the current efficiency reaches the maximum value of 21.5 cd.A -1 。
The variation trend of the power efficiency of the electroluminescent red device 2 along with the change of the brightness is tested to obtain that the brightness of the device is 2.54 cd.m -2 When the current efficiency reaches the maximum value of 24.6 cd.A -1 。
Testing the variation trend of external quantum efficiency of the electroluminescent red device 2 to the change of current density to obtain the brightness of the device of 2.54 cd.m -2 Then, a maximum external quantum efficiency of 16.4% was obtained.
The electroluminescence spectrum of the electroluminescent red device 2 is shown in FIG. 6, from which it can be seen that the electroluminescence peak of the device is at 608 nm.
Example 3
(1) Intermediate i was prepared according to the procedure in example 2.
(2) 1mmol of the intermediate I, 5mmol of cuprous cyanide and 20mL of N, N-dimethylformamide are mixed and reacted for 12 hours at the temperature of 140 ℃. Then pouring a mixed solution of 2M ferric trichloride and hydrochloric acid and dichloromethane for extraction, drying, removing the organic solvent to obtain a crude product, and performing column chromatography purification by using a mixed solvent of petroleum ether and dichloromethane (the volume ratio of the two is 1.
The results of the nuclear magnetic resonance test of compound 3 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)。
thermogravimetric analysis of compound 3 revealed a cracking temperature of 445 ℃.
The electroluminescent device 3 is prepared according to the method of embodiment 1, and has the following structure: 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).
By testing the variation trend of the current density of the electroluminescent device 3 with the voltage, the compound 3 is known to have semiconductor characteristics, and the threshold voltage thereof is 3.4V.
The variation trend of the brightness of the electroluminescent red device 3 along with the voltage change is tested, and the maximum brightness of the device can reach 16233 cd.m -2 。
The current efficiency of the electroluminescent device 3 is tested to obtain the change trend of the device in the luminance of 2.9 cd.m -2 When the current efficiency reaches the maximum value of 19.6 cd.A -1 。
Testing the variation trend of the power efficiency of the electroluminescent red device 3 along with the change of the brightness to obtain the device with the brightness of 2.9 cd.m -2 When the power efficiency reaches the maximum value of 18.3 lm.W -1 。
Testing the variation trend of external quantum efficiency of the electroluminescent device 3 to the change of current density to obtain the brightness of the device of 2.9 cd.m -2 Then, a maximum external quantum efficiency of 18.8% was obtained.
The electroluminescence spectrum of the red electroluminescent device 3 is shown in FIG. 7, from which it can be seen that the electroluminescence peak of the device is at 632 nm.
Example 4
(1) Intermediate i was prepared according to the procedure 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 12 hours. Then 2M ammonium chloride aqueous solution and dichloromethane are poured for extraction, organic solvent is removed after drying, crude product is obtained, mixed solvent of petroleum ether and dichloromethane is used as eluent for column chromatography purification, and compound 4 (4, 4' - (dithiophene [2,3-a:3',2' -c ] phenazine-2, 5,9, 10-tetra-yl) tetra (N, N-diphenylaniline)) is obtained.
The results of the nuclear magnetic resonance test of compound 4 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)。
thermogravimetric analysis of compound 4 revealed that the cleavage temperature was 467 ℃.
An electroluminescent 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).
By testing the variation trend of the current density of the electroluminescent device 4 with the voltage, the compound 4 is known to have semiconductor characteristics, and the threshold voltage thereof is 3.3V.
The variation trend of the brightness of the electroluminescent red light device 4 along with the voltage change is tested, and the maximum brightness of the device can reach 17866 cd.m -2 。
The current efficiency of the electroluminescent red device 4 is tested to obtain the change trend of the device with the brightness of 3.4 cd.m -2 When the current efficiency reaches the maximum value of 18.3 cd.A -1 。
Testing the variation trend of the power efficiency of the electroluminescent red device 4 along with the change of the brightness to obtain the device with the brightness of 3.4 cd.m -2 When the power efficiency reaches the maximum value of 16.9 lm.W -1 。
The variation trend of the external quantum efficiency of the electroluminescent red device 4 to the change of the current density is tested to obtain the brightness of the device of 3.4 cd.m -2 Then, maximum external quantum efficiency is obtained16.6％。
The electroluminescence spectrum of the electroluminescent red device 4 is shown in FIG. 8, from which it can be seen that the electroluminescence peak of the device is 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 12 hours. After the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, removing the organic solvent, and performing column chromatography purification by using a mixed solvent of dichloromethane and petroleum ether (the volume ratio of the two solvents is 1:
(2) 1mmol of 4- (6-bromobenzo [ c ] was taken][1,2,5]Thiadiazol-5-yl) -N, N-diphenylaniline, 0.005mmol of palladium acetate, 2mmol of sodium acetate, 2mmol of diphenylphosphine and 20mL of N, N-dimethylformamide are mixed, reacted at the temperature of 135 ℃ for 12 hours, and then 5mmol of H is added 2 O 2 And (2) oxidizing, after the reaction is finished, adding water and dichloromethane for extraction, combining organic layers, drying, removing the organic solvent, and performing column chromatography purification by using a mixed solvent of dichloromethane and methanol (the volume ratio of the dichloromethane to the methanol is 60)][1,2,5]Thiadiazol-5-yl) diphenylphosphine 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 respectively, reacting at 80 ℃ for 48h, extracting with water and dichloromethane, combining organic layers, drying, and purifying by using a mixed solvent of dichloromethane and ethyl acetate as an eluent column chromatography 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 mixed, reacted at 120 ℃ for 12h, extracted with water and dichloromethane, the organic layers are combined, dried and purified by column chromatography with a mixed solvent of dichloromethane and ethyl acetate (the volume ratio of the two is 8.
The results of the nuclear magnetic resonance test of compound 5 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 ultraviolet absorption spectrum and photoluminescence spectrum (fluorescence spectrum) of the toluene solution of the compound 5 and the thin film of the compound 5 were measured, as shown in FIG. 3.
The thermogravimetric analysis of compound 5 showed that the cleavage temperature was 445 ℃ as shown in FIG. 4.
An electroluminescent 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). .
By testing the variation trend of the current density of the electroluminescent device 5 with the voltage, the compound 5 is known to have semiconductor characteristics, and the threshold voltage thereof is 4.4V.
The trend of the change of the brightness of the electroluminescent red device 5 with the change of the voltage is tested, and as shown in FIG. 13, the maximum brightness of the device can reach 7955 cd-m -2 。
The trend of the current efficiency of the electroluminescent device 5 with the change of luminance was examined, as shown in FIG. 14, to obtain a luminance of 2.7 cd-m -2 When the current efficiency reaches the maximum value of 8.96 cd.A -1 。
The trend of the power efficiency of the electroluminescent device 5 with the change of the luminance was tested, as shown in FIG. 15, to obtain the luminance of the device at 2.7cd m -2 When the power efficiency reaches the maximum value of 5.21 lm.W -1 。
The trend of variation of external quantum efficiency to luminance change of the electroluminescent device 5 was tested, as shown in FIG. 16, to obtain a luminance of 2.7 cd. M -2 Then, the maximum external quantum efficiency of 8.0% was obtained.
The electroluminescence spectrum of the electroluminescent red device 5 is shown in FIG. 9, from which it can be seen that the electroluminescence peak of the device is at 632 nm.
Example 6
(1) Intermediate II was prepared according to the procedure for the preparation of the compound of example 5. The only difference is that: the benzodithiophene-4, 5-dione was replaced with an equimolar amount of 2, 7-dibromobenzodithiophene-4, 5-dione. An intermediate II:
(2) Mixing the intermediate II obtained in the step 1mmol, 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 (4) oxidizing. After the reaction, water and dichloromethane were added for extraction, the organic layers were combined, dried and then the organic solvent was removed, and column chromatography was performed using a mixed solvent of dichloromethane and methanol (the volume ratio of the two was 50]Phenazine-2, 5, 9-triyl) tris (diphenylphosphine oxide)).
The results of the compound 6 nmr 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)。
thermogravimetric analysis of Compound 6 revealed that the cleavage temperature was 426 ℃.
Device 6 was prepared as in example 5: ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 6 (20%) was 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The current density of the electroluminescent device 6 is tested to change along with the change of the voltage, and the compound 6 is known to have semiconductor characteristics, and the threshold voltage of the compound is 3.6V.
The variation trend of the brightness of the electroluminescent red device 6 along with the change of the voltage is tested, and the maximum brightness of the device can reach 15467 cd.m -2 。
The current efficiency of the electroluminescent red device 6 is tested to change with the change of the brightness, and the brightness of the device is 2.77 cd.m -2 When the current efficiency reaches the maximum value of 15.7 cd.A -1 。
Testing the variation trend of the power efficiency of the electroluminescent red device 6 along with the change of the brightness to obtain the device with the brightness of 2.77 cd.m -2 When the power efficiency reaches the maximum value of 14.4 lm.W -1 。
The variation trend of the external quantum efficiency of the electroluminescent red device 6 to the change of the current density is tested to obtain the brightness of the device of 2.77 cd.m -2 Then, the maximum external quantum efficiency of 19.2% is obtained.
The electroluminescence spectrum of the red electroluminescent device 6 is shown in FIG. 10, from which it can be seen that the electroluminescence peak of the device is at 648 nm.
Example 7
(1) Intermediate ii was prepared according to the procedure in example 6.
(2) 1mmol of the intermediate II, 5mmol of cuprous cyanide and 20ml of N, N-dimethylformamide are mixed and reacted for 12 hours at the temperature of 140 ℃. Then pouring a mixed solution of ferric trichloride and hydrochloric acid and dichloromethane for extraction, drying, removing an organic solvent to obtain a crude product, and performing column chromatography purification by using a mixed solvent of dichloromethane and ethyl acetate (the volume ratio of the two is 6.
The results of the nuclear magnetic resonance test of compound 7 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).
thermogravimetric analysis was performed on the obtained compound 7, and the cracking temperature of the obtained compound was 420 ℃.
According to the preparation method of the electroluminescent device 1 in the embodiment 1, the electroluminescent device 7 is prepared by taking the mixture of the compound 7 and the CBP (wherein, the mass fraction of the compound 7 is 20%) as a luminescent layer material, and the structure of the electroluminescent device 7 is ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 7 (20%) was 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
By testing the variation trend of the current density of the electroluminescent device 7 with the voltage, the compound 7 is known to have semiconductor characteristics, and the threshold voltage thereof is 3.1V.
The variation trend of the brightness of the electroluminescent red light device 7 along with the voltage change is tested, and the maximum brightness of the device can reach 14473 cd.m -2 。
The current efficiency of the electroluminescent red device 7 is tested to change with the change of the brightness, and the brightness of the device is 3.2 cd.m -2 When the current efficiency reaches the maximum value of 15.3 cd.A -1 。
Testing the variation trend of the power efficiency of the electroluminescent red device 7 along with the change of the brightness to obtain the device with the brightness of 3.2 cd.m -2 When the power efficiency reaches the maximum value of 15.7 lm.W -1 。
The variation trend of the external quantum efficiency of the electroluminescent red device 7 to the change of the current density is tested to obtain the brightness of the device of 3.2 cd.m -2 Then, a maximum external quantum efficiency of 23.7% was obtained.
The electroluminescence spectrum of the electroluminescent red device 7 is shown in FIG. 11, from which it can be seen that the electroluminescence peak of the device is 660nm.
Example 8
(1) Intermediate ii was synthesized according to example 6.
(2) 1mmol of intermediate II, 2mmol of triphenylamine-4-boronic acid, 0.025mmol of tetrakis (triphenylphosphine) palladium, 0.2mmol of tetrabutylammonium bromide, 6mmol of sodium hydroxide and 20mL of toluene are mixed and reacted at 110 ℃ for 12 hours. Then 2M ammonium chloride aqueous solution and dichloromethane are poured for extraction, organic solvent is removed after drying, crude product is obtained, mixed solvent of dichloromethane and methanol (the volume ratio of the two is 20.
The obtained compound 8 is subjected to nuclear magnetic resonance hydrogen spectrum analysis, and the test data is 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).
thermogravimetric analysis was performed on the obtained compound 8, and the cracking temperature of the obtained compound was 433 ℃.
According to the preparation method of the electroluminescent device in the embodiment 1, the electroluminescent device 8 is prepared by taking the mixture of the compound 8 and the CBP (wherein the mass fraction of the compound 8 is 20%) as a luminescent layer material, and the structure of the electroluminescent device is ITO/MoO 3 (6 nm)/NPB (50 nm)/TCTA (5 nm)/CBP: compound 8 (20%) 20nm/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm).
The trend of the current density of the electroluminescent device 8 changing with the voltage is tested, and the compound 8 is known to have semiconductor characteristics, and the threshold voltage of the compound is 3.2V.
The variation trend of the brightness of the electroluminescent red light device 8 along with the voltage change is tested, and the maximum brightness of the device can reach 10354 cd-m -2 。
The current efficiency of the electroluminescent red light device 8 is tested to obtain the change trend of the current efficiency with the change of the brightness, 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 variation trend of the power efficiency of the electroluminescent red device 8 along with the change of the 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 external quantum efficiency of an electroluminescent device 8The variation trend of the current density change is to obtain the brightness of the device at 3.4 cd.m -2 Then, a maximum external quantum efficiency of 20.2% was obtained.
The electroluminescence spectrum of the electroluminescent red device 8 is shown in FIG. 12, from which it can be seen that the electroluminescence peak of the device is at 640nm.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate 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, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A compound based on a dithiophene phenazine receptor, wherein the dithiophene phenazine receptor is used as a matrix, and one or more substituents of a nitrogen-containing aryl group, an aromatic phosphine oxide group and a cyano group are used as donors.
2. The compound of claim 1, wherein the compound has the general formula:
wherein, X 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinoxy groups, preferably aryl-substituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably selected from diphenylaminophenyl or diphenylphosphinoxy;
R 1 、R 2 each independently selected from hydrogen, cyano, nitrogen-containing aryl or aromatic phosphinoxy groups, preferably hydrogen, cyano, aryl-substituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably hydrogen, cyano, diphenylaminophenyl or diphenylphosphinoxy.
3. The compound according to claim 1, wherein the dithienophenoxazine receptor based compound is selected from one of compounds 1 to 8, compounds 1 to 8 being in particular as follows:
4. a method for preparing a dithienophenazine-receptor-based compound according to any one of claims 1 to 3, characterized in that 5, 6-dihalobenzo [ c ] [1,2,5] thiadiazole is used as a starting material to prepare an anthrancene compound, which is then cyclized with a benzodithiophene-4, 5-dione compound to obtain a dithienphenazine-receptor-based compound; or 5, 6-dihalogenobenzo [ c ] [1,2,5] thiadiazole is used as an initial material to prepare an o-aminobenzene compound, then the o-aminobenzene compound and benzodithiophene-4, 5-diketone compound are subjected to ring closure, and a nitrogen-containing aryl group, an aromatic phosphine oxide group or a cyano group are grafted to obtain a compound based on a dithiophene phenazine receptor;
the o-aminobenzene compound has the following structure:
wherein, X 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinoxy groups, preferably selected from aryl-substituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably diphenylaminophenyl or diphenylphosphinoxy;
preferably, the o-aminobenzene compound is 4-nitrogen-containing aryl-5-aromatic phosphinoxy o-phenylenediamine or 4, 5-bis-nitrogen-containing aryl o-phenylenediamine, wherein the nitrogen-containing aryl is preferably aryl substituted aminophenyl, and the aromatic phosphinoxy is preferably phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably, the o-aminobenzene compound is 4- (4-diphenylamino) phenyl-5-diphenylphosphinoxy o-phenylenediamine or 4, 5-bis (4-diphenylamino) phenyl-o-phenylenediamine;
the benzodithiophene-4, 5-dione compound is benzodithiophene-4, 5-dione or 2, 7-dihalobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-dione, and the halogenation is bromination, iodo or chlorination, preferably bromination.
5. Method according to claim 4, characterized in that it comprises the following steps:
step 1, preparing an o-aminobenzene compound from 5, 6-dihalogenobenzo [ c ] [1,2,5] thiadiazole;
step 2, performing a 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 the compound based on the dithiophene phenazine receptor.
6. The method of claim 5,
in step 1, the 5, 6-dihalogenobenzo [ c ] [1,2,5] thiadiazole is reacted with an aromatic amine boron compound to obtain 5, 6-dinitrodiazoarylbenzo [ c ] [1,2,5] thiadiazole or 5-nitrogenous aryl-6-halobenzo [ c ] [1,2,5] thiadiazole;
reducing the 5, 6-dinitrogen-containing aryl benzo [ c ] [1,2,5] thiadiazole to obtain 4, 5-dinitrogen-containing aryl o-phenylenediamine;
the 5-nitrogen-containing aryl-6-halogenobenzo [ c ] [1,2,5] thiadiazole reacts with an aromatic phosphine compound, the 5-nitrogen-containing aryl-6-aromatic phosphinyloxybenzo [ c ] [1,2,5] thiadiazole is obtained through oxidation and oxidation of hydrogen, and then the 4-nitrogen-containing aryl-5-aromatic phosphinyloxy o-phenylenediamine is obtained through reduction.
7. The method according to claim 5, wherein, in step 2,
the benzodithiophene-4, 5-diketone compound is benzodithiophene-4, 5-diketone, the o-aminobenzene compound is 4, 5-dinitro-nitrogen-containing aryl o-phenylenediamine or 4-dinitro-nitrogen-containing aryl-5-aromatic phosphino-o-phenylenediamine, and a compound 1 or a compound 5 is obtained through reaction;
the benzodithiophene-4, 5-diketone compound is 2, 7-dihalogenobenzo [1,2-B:6,5-B' ] dithiophene-4, 5-diketone, the o-aminobenzene compound is 4, 5-dinitro-nitrogen-containing aryl o-phenylenediamine or 4-dinitro-nitrogen-containing aryl-5-aromatic phosphino-o-phenylenediamine, and an intermediate is obtained through reaction,
the intermediate is as follows:
wherein, X 0 Is chlorine, iodine or bromine, preferably bromine; x 1 、X 2 Each independently selected from nitrogen-containing aryl or aromatic phosphinoxy groups, preferably aryl-substituted aminophenyl, phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably diphenylaminophenyl or diphenylphosphinoxy; more preferably, X 1 、X 2 Are both diphenylaminophenyl or X 1 Is diphenylaminophenyl, X 2 Is diphenylphosphinyloxy.
8. The method according to claim 8, wherein, in step 3,
the aromatic amine compound is selected from aryl-substituted aminobenzene-4-boronic acid pinacol ester or aryl-substituted aminobenzene-4-boronic acid, preferably triphenylamine-4-boronic acid pinacol ester or triphenylamine-4-boronic acid, the intermediate reacts with the aromatic amine compound to obtain the compound based on the dithiophene phenazine receptor, and at this time,
in, R 1 、R 2 Are each a nitrogen-containing aryl group, preferably an aminoaryl group, more preferably a diPhenylaminophenyl, such as compound 4, compound 8;
the aromatic phosphine oxide compound is phenyl phosphine, diphenyl phosphine or triphenyl phosphine, and preferably diphenyl phosphine; the intermediate reacts with the aromatic phosphine oxide compound to yield a compound based on the dithienophenazine receptor, and at this time,
in, R 1 、R 2 Are both aromatic phosphinoxy groups, preferably phenylphosphinoxy, diphenylphosphinoxy or triphenylphosphine oxy, more preferably diphenylphosphinoxy, such as compound 2, compound 6;
the cyano compound is selected from metal cyanide, preferably one or more of cuprous cyanide, sodium hydride and potassium hydride, and more preferably cuprous cyanide; the intermediate is reacted with a cyano compound to give a compound based on a dithienophenazine receptor, in which case,
in, R 1 、R 2 Both cyano groups, such as compound 3, compound 7.
9. Use of a dithienophenoxazine receptor-based compound according to claim 1 as a light-emitting layer material for the preparation of electroluminescent red devices having a luminance of 7500-26000 cd-m -2 The external quantum efficiency is 5% -24%, and the electroluminescent wavelength is 580-660nm.
10. An electroluminescent device, characterized in that the material of the light-emitting layer of the electroluminescent device comprises the dithienophenoxazine receptor based compound, preferably compound 1-compound 8, more preferably compounds 5 to 8.
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