CN111675693A - D-A type luminous micromolecules containing acridine and phenanthroimidazole and application thereof in electroluminescent device - Google Patents
D-A type luminous micromolecules containing acridine and phenanthroimidazole and application thereof in electroluminescent device Download PDFInfo
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Abstract
The invention discloses an electron donor-acceptor D-A type luminescent micromolecule containing acridine and phenanthroimidazole and application thereof in an electroluminescent device. According to the invention, an acridine electron donor unit and a phenanthroimidazole electron acceptor unit are respectively connected to two sides of an anthracene unit with large steric hindrance, the donor unit and the acceptor unit in the constructed molecule have larger torsion angles, and moderate charge transfer is realized, so that a Hybrid Local Charge Transfer (HLCT) excited state is formed, cross from a high-energy triplet state to a singlet state and intersystem crossing can be realized, and one hundred percent utilization of excitons is realized. In addition, the acridine and the phenanthroimidazole have the characteristics of wide band gap, high fluorescence quantum yield and high carrier mobility, and the light-emitting small molecule containing the acridine and the phenanthroimidazole can be used for preparing a high-efficiency blue organic electroluminescent device.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a D-A type luminous micromolecule containing acridine and phenanthroimidazole and application thereof in an electroluminescent device.
Background
Organic Light Emitting Diodes (OLEDs) have the advantages of being flexible, actively emitting light, high efficiency, driven at low voltage, and easily fabricated into large-area devices, and have received much attention from people. The research related to the OLED can be traced back to 60 years in the 20 th century, 1963, professor Pope of New York university and the like, the electroluminescence phenomenon of organic molecular single crystal anthracene is discovered for the first time, and then some researches on the electroluminescence performance of single crystal structure materials are sequentially carried out, but the research cannot attract wide attention due to the high driving voltage of the devices at that time. Until 1987, Duncong cloud et al of Kodak corporation in USA developed OLED device with sandwich structure and brightness of 1000cd m under 10V DC voltage drive-2This has led to an epoch-making development in OLED research.
The organic light emitting diode has two main application prospects: one is applied to novel displays and the other is applied to solid state lighting. The light emitting material is the most central part of the OLED, determines the device emission color, and to a large extent, device efficiency and device lifetime. To realize a full-color display panel with a high color rendering index, organic light emitting materials emitting three colors of red, green and blue are required. Compared with green light and red light materials, the blue fluorescent material with high efficiency is still deficient, so that the development of a novel blue light material with high performance is a research focus of OLED research.
The conventional fluorescent material can emit light by using only 25% of singlet excitons, so that the light emitting performance is greatly limited. In order to solve the problem of low exciton utilization, phosphorescent materials utilizing triplet exciton emission, thermal activation delayed fluorescence TADF materials based on triplet-to-intersystem crossing, and TTA fluorescent materials based on triplet-to-triplet annihilation up-conversion have been developed. However, the first two types of materials have few high efficiency materials satisfying the blue color coordinate CIEy <0.15, and moreover, the two types of materials also face serious efficiency roll-off problems, which are not favorable for practical applications (Science Chinese Chemistry,2014,57, 335-. The TTA fluorescent material forms a singlet exciton by fusing two triplet excitons, and the exciton utilization rate is only 62.5%. Besides the materials, the fluorescent material has the characteristic of hybridization local charge transfer excited state, and the thermal exciton material based on the high-energy charge transfer state can realize the reverse intersystem crossing from a high triplet state energy level to a singlet state energy level, realize the full utilization of excitons and provide a new idea for the development of high-performance blue fluorescent materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a D-A type luminescent small molecule containing acridine and phenanthroimidazole and application thereof in an electroluminescent device.
The invention aims to provide a D-A type luminous micromolecule containing acridine and phenanthroimidazole and application thereof in an electroluminescent device. The acridine and phenanthroimidazole units are units with wide band gap, high stability, high fluorescence quantum yield and high carrier mobility, and have asymmetric molecular structures which can inhibit molecular aggregation.
The purpose of the invention is realized by at least one of the following technical solutions.
A D-A type luminous micromolecule containing acridine and phenanthroimidazole has a chemical structural formula satisfying one of the following structures:
wherein R is H, F, CN and alkyl with 1-4 carbon atoms; r' is methyl or phenyl.
The D-A type luminous micromolecule containing acridine and phenanthroimidazole can be used as a luminous layer for preparing an organic light-emitting diode device.
Furthermore, the D-A type light-emitting micromolecules containing acridine and phenanthroimidazole are applied to the organic electroluminescent device, the organic electroluminescent device has a structure of an anode/a hole injection layer/a hole transport layer/a light-emitting layer/an electron transport layer/an electron injection layer/a cathode, and the organic light-emitting layer at least contains one light-emitting micromolecule containing acridine and phenanthroimidazole. The light-emitting layer is a pure film of light-emitting micromolecules containing acridine and phenanthroimidazole or a mixed film doped with the light-emitting micromolecules containing acridine and phenanthroimidazole and a host material.
The principle of the invention is as follows: acridine is used as an electron donor unit, phenanthroimidazole is used as an electron acceptor unit, and a novel donor-acceptor type blue fluorescent molecule is constructed. The molecule has the characteristics of wide band gap of acridine unit, high fluorescence quantum yield, high hole mobility, large conjugated rigid structure of the phenanthroimidazole, high fluorescence quantum yield and high electron mobility. Moreover, the molecules have moderate charge transfer degree, can form hybrid local charge transfer state (HLCT) luminescence, and improve the exciton utilization rate. In addition, the molecules have asymmetric structures, and can inhibit molecular aggregation and reduce exciton quenching.
According to the invention, an acridine electron donor unit and a phenanthroimidazole electron acceptor unit are respectively connected to two sides of an anthracene unit with large steric hindrance, the donor unit and the acceptor unit in the constructed molecule have larger torsion angles, and moderate charge transfer is realized, so that a Hybrid Local Charge Transfer (HLCT) excited state is formed, cross from a high-energy triplet state to a singlet state and intersystem crossing can be realized, and one hundred percent utilization of excitons is realized. In addition, the acridine and the phenanthroimidazole have the characteristics of wide band gap, high fluorescence quantum yield and high carrier mobility, and the light-emitting small molecule containing the acridine and the phenanthroimidazole can be used for preparing a high-efficiency blue organic electroluminescent device.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the luminous micromolecules containing acridine and phenanthroimidazole, an acridine electron-donating unit and a phenanthroimidazole electron-withdrawing unit are respectively coupled to two sides of an anthracene unit, so that the luminous micromolecules have larger steric hindrance, have larger torsion angles among the electron-donating units and the receptor units, form a charge transfer state with moderate strength, can be hybridized with a local state of a molecule to form Hybrid Local Charge Transfer (HLCT) charge transfer excited state luminescence, and realize high exciton utilization rate;
(2) the luminous micromolecules containing acridine and phenanthroimidazole provided by the invention can adjust the steric hindrance and charge transfer degree of the molecules by adjusting the coupling sites, end groups and the like of acridine and phenanthroimidazole units, so that the emission spectrum is changed, and the intersystem crossing from triplet excitons to singlet excitons is improved;
(3) according to the light-emitting micromolecules containing acridine and phenanthroimidazole, the acridine and the phenanthroimidazole are respectively used as electron donor/acceptor units, and the constructed D-A type molecule has good hole and electron injection and transmission capacity and has the characteristic of bipolar transmission;
(4) the acridine and the phenanthroimidazole are wide band gap units, so that the current shortage of blue fluorescent molecules can be constructed, and the two units have higher fluorescence quantum yield and are expected to realize high efficiency.
Drawings
FIG. 1 is a graph of Stokes shift of small molecule M3 in different solvents as a function of solvent polarizability;
FIG. 2 is an electroluminescence spectrum of a small molecule M4 under a doped device structure;
fig. 3 is a current density-voltage curve of the small molecule M5 under a doped device structure;
fig. 4 is a current efficiency-current density curve of the small molecule M6 under the structure of a doped device.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Preparation of Compound M1
The structural formula and the synthetic route of the compound M1 are shown in the following figure, and the specific synthetic method is as follows:
(1) synthesis of Compound 1
Under the protection of nitrogen, 9, 10-dihydro-9, 9-diphenylacridine (10mmol), 9, 10-dibromoanthracene (10mmol), sodium tert-butoxide (25mmol) and a catalyst of tris-dibenzylideneacetone dipalladium (Pd)2(dba)30.5mmol) and ligand tri-tert-butylphosphine (1mmol) were added to 50ml of toluene, stirred and heated to 120 ℃ for 10 hours. After the reaction is finished, extracting the product by using ethyl acetate, washing the product for three times by using a saturated sodium chloride solution, drying the product by using anhydrous sodium sulfate, filtering the dried solution, and spin-drying the solvent by using a rotary evaporator to obtain a crude product. Separating and purifying the crude product by using a silica gel chromatographic column, wherein the eluent selects a petroleum ether/dichloromethane mixed solvent to obtain a white solid product with the yield of 66%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Synthesis of Compound 2
Under the protection of nitrogen, phenanthrenequinone (10mmol), p-bromobenzaldehyde (10mmol), aniline (10mmol) and trimethylamine hydrochloride (30mmol) were added to 80ml of acetic acid, and the mixture was heated to reflux for 24 hours. Cooling to room temperature, standing, performing suction filtration, and washing filter residues with ethanol for 3 times to obtain a crude product. Recrystallization from a tetrahydrofuran/ethanol mixed solvent gave the product as a white solid in 79% yield.1HNMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(3) Synthesis of Compound 3
Under a nitrogen atmosphere, compound 2(10mmol), pinacol diboron diboride (12mmol), potassium acetate (30mmol) and [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (0.5mmol) was added to 50ml1, 4-dioxane, warmed to 80 ℃ and reacted 12And (4) hours. After the reaction is finished, cooling, distilling under reduced pressure, spin-drying the reaction solvent, extracting with dichloromethane, washing with saturated sodium chloride solution for 3 times, and purifying the crude product by using petroleum ether/dichloromethane as eluent column chromatography to obtain a white solid product with the yield of 81%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Synthesis of Compound M1
Under the protection of nitrogen, compound 1(10mmol), compound 3(10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 50ml of toluene and 15ml of water, tetrabutylammonium bromide (0.3mmol) is added as a phase transfer catalyst, and the temperature is raised to 85 ℃ for reaction for 8 hours. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and the solid product is obtained after purification, wherein the yield is 73%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. The fluorescence quantum yield of compound M1 was 91% as measured by an integrating sphere.
Example 2
Preparation of Compound M2
The structural formula and the synthetic route of the compound M2 are shown in the following figure, and the specific synthetic method is as follows:
(1) synthesis of Compound 4
Under the protection of nitrogen, 9, 10-dihydro-9, 9-dimethylacridine (10mmol), 1, 4-dibromobenzene (10mmol), sodium tert-butoxide (25mmol) and a catalyst of palladium (Pd) tris (dibenzylideneacetone)2(dba)30.5mmol) and ligand tri-tert-butylphosphine (1mmol) were added to 50ml of toluene, stirred and heated to 120 ℃ for 10 hours. After the reaction is finished, extracting the product by ethyl acetate, washing the product for three times by saturated sodium chloride solution, and using anhydrous sulfurThe sodium salt was dried, the dried solution was filtered and the solvent was spun off using a rotary evaporator to give the crude product. And separating and purifying the crude product by using a silica gel chromatographic column, wherein the eluent is a petroleum ether/dichloromethane mixed solvent to obtain a white solid product with the yield of 73%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Synthesis of Compound 5
Under a nitrogen atmosphere, a reactant 4(10mmol), pinacol diboron diboride (12mmol), potassium acetate (10mmol) and [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl20.5mmol) was added to the reaction and dissolved with 100mL1, 4-dioxane, warmed to 80 ℃ and reacted for 12 hours. After the reaction is finished, washing with water after spin-drying reaction, then extracting with dichloromethane, and purifying the crude product by column chromatography with a petroleum ether/dichloromethane mixed solvent as an eluent to obtain a white solid product with the yield of 84%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Synthesis of Compound 6
Under the protection of nitrogen, compound 5(10mmol), 9, 10-dibromoanthracene (10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 50ml of toluene and 15ml of water, tetrabutylammonium bromide (0.3mmol) is added as a phase transfer catalyst, and the temperature is raised to 85 ℃ for reaction for 8 hours. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and a white solid product is obtained after purification, wherein the yield is 68%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Synthesis of Compound M2
Under the protection of nitrogen, compound 6(10mmol), compound 3(10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 50ml of toluene and 15ml of water, and tetrabutylammonium bromide is added(0.3mmol) as a phase transfer catalyst, and heating to 85 ℃ for reaction for 8 hours. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and the solid product is obtained after purification, wherein the yield is 83%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. The fluorescence quantum yield of compound M2 was determined by integrating sphere to be 95%.
Example 3
Preparation of Compound M3
The structural formula and the synthetic route of the compound M3 are shown as follows, and the specific synthetic method is as follows:
(1) synthesis of Compound 7
Under the protection of nitrogen, 9, 10-dihydro-9, 9-dimethylacridine (10mmol), 1, 3-dibromobenzene (10mmol), sodium tert-butoxide (25mmol) and a catalyst of palladium (Pd) tris (dibenzylideneacetone)2(dba)30.5mmol) and ligand tri-tert-butylphosphine (1mmol) were added to 50ml of toluene, stirred and heated to 120 ℃ for 10 hours. After the reaction is finished, extracting the product by using ethyl acetate, washing the product for three times by using a saturated sodium chloride solution, drying the product by using anhydrous sodium sulfate, filtering the dried solution, and spin-drying the solvent by using a rotary evaporator to obtain a crude product. And separating and purifying the crude product by using a silica gel chromatographic column, wherein the eluent is a petroleum ether/dichloromethane mixed solvent to obtain a white solid product with the yield of 76%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(2) Synthesis of Compound 8
Under a nitrogen atmosphere, the reaction product 7(10mmol), pinacol diboron diboride (12mmol), potassium acetate (10mmol) and [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl20.5mmol) was added to the reaction and dissolved with 100mL1, 4-dioxane, warmed to 80 ℃ and reacted for 12 hours. After the reaction is finished, washing with water after spin-drying reaction, then extracting with dichloromethane, and purifying the crude product by column chromatography with a petroleum ether/dichloromethane mixed solvent as an eluent to obtain a white solid product with the yield of 88%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Synthesis of Compound 9
Under the protection of nitrogen, compound 8(10mmol), 9, 10-dibromoanthracene (10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 50ml of toluene and 15ml of water, tetrabutylammonium bromide (0.3mmol) is added as a phase transfer catalyst, and the temperature is raised to 85 ℃ for reaction for 8 hours. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and a white solid product is obtained after purification, wherein the yield is 71%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(4) Synthesis of Compound M3
Under the protection of nitrogen, compound 9(10mmol), compound 3(10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 50ml of toluene and 15ml of water, tetrabutylammonium bromide (0.3mmol) is added as a phase transfer catalyst, and the temperature is raised to 85 ℃ for reaction for 8 hours. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and the solid product is obtained after purification, wherein the yield is 89%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. The fluorescence quantum yield of compound M3 was 97% as measured by integrating sphere.
FIG. 1 is a graph of Stokes shift of a small molecule M3 in different solvents and solvent polarizability, and it can be found that two straight lines with different slopes can be fitted to the Stokes shift relative to the solvent polarizability, which indicates that the molecule exists in both a local state and a charge transfer state.
Example 4
Preparation of Compound M4
The structural formula and the synthetic route of the compound M4 are shown in the following figure, and the specific synthetic method is as follows
(1) Synthesis of Compound 10
Phenanthrenequinone (10mmol), p-fluorobenzaldehyde (10mmol), p-bromoaniline (10mmol) and trimethylamine hydrochloride (30mmol) are added to 100ml of acetic acid under the protection of nitrogen, and the mixture is heated to reflux for 24 hours. Cooling to room temperature, standing, performing suction filtration, and washing filter residues with ethanol for 3 times to obtain a crude product. Recrystallization from a tetrahydrofuran/ethanol mixed solvent gave the product as a white solid in 85% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Synthesis of Compound 11
Under a nitrogen atmosphere, compound 10(10mmol), pinacol diboron diboride (12mmol), potassium acetate (30mmol) and [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (0.5mmol) was added to 50ml1, 4-dioxane, warmed to 80 ℃ and reacted for 12 hours. After the reaction is finished, cooling, distilling under reduced pressure, spin-drying the reaction solvent, extracting with dichloromethane, washing with saturated sodium chloride solution for 3 times, and purifying the crude product by using petroleum ether/dichloromethane as eluent column chromatography to obtain a white solid product with the yield of 75%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Synthesis of Compound M4
Under the protection of nitrogen, compound 1(10mmol), compound 11(10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 50ml of toluene and 15ml of water, and then tetrakis (triphenylphosphine) is addedButyl ammonium bromide (0.3mmol) as phase transfer catalyst, and heating to 85 deg.C for 8 hr. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and the solid product is obtained after purification, wherein the yield is 76%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. The fluorescence quantum yield of compound M4 was measured by integrating sphere to be 90%.
Example 5
Preparation of Compound M5
The structural formula and the synthetic route of the compound M5 are shown in the following figure, and the specific synthetic method is as follows
(1) Synthesis of Compound 12
Phenanthrenequinone (10mmol), p-cyanobenzaldehyde (10mmol), p-bromoaniline (10mmol) and trimethylamine hydrochloride (30mmol) were added to 100ml of acetic acid under nitrogen protection, and the mixture was heated to reflux for 24 hours. Cooling to room temperature, standing, performing suction filtration, and washing filter residues with ethanol for 3 times to obtain a crude product. Recrystallization from a tetrahydrofuran/ethanol mixed solvent gave the product as a white solid in 75% yield.1H NMR、13The results of CNMR, MS and elemental analysis show that the obtained compound is a target product.
(2) Synthesis of Compound 13
Under a nitrogen atmosphere, compound 12(10mmol), pinacol diboron diboride (12mmol), potassium acetate (30mmol) and [1, 1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (0.5mmol) was added to 50ml1, 4-dioxane, warmed to 80 ℃ and reacted for 12 hours. After the reaction is finished, cooling, distilling under reduced pressure, spin-drying the reaction solvent, extracting with dichloromethane, washing with saturated sodium chloride solution for 3 times, and purifying the crude product by using petroleum ether/dichloromethane as eluent column chromatography to obtain a white solid product with the yield of 82%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
(3) Synthesis of Compound M5
Under the protection of nitrogen, compound 6(10mmol), compound 13(10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 50ml of toluene and 15ml of water, tetrabutylammonium bromide (0.3mmol) is added as a phase transfer catalyst, and the temperature is raised to 85 ℃ for reaction for 8 hours. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and the solid product is obtained after purification, wherein the yield is 70%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. The fluorescence quantum yield of compound M5 was 94% as measured by an integrating sphere.
Example 6
Preparation of Compound M6
The structural formula and the synthetic route of the compound M6 are shown in the following figure, and the specific synthetic method is as follows
Under the protection of nitrogen, compound 9(10mmol), compound 13(10mmol), potassium carbonate (30mmol) and tetrakis (triphenylphosphine) palladium (0.5mmol) are dissolved in 60ml of toluene and 15ml of water, tetrabutylammonium bromide (0.3mmol) is added as a phase transfer catalyst, and the temperature is raised to 85 ℃ for reaction for 8 hours. After the reaction is finished, the toluene solvent is removed by reduced pressure distillation, the product is extracted by dichloromethane, the product is washed by saturated sodium chloride aqueous solution for three times, the solvent is removed by an organic phase through a rotary evaporator, the crude product is purified by a column chromatography method, silica gel is used as a stationary phase, petroleum ether/dichloromethane is used as a mobile phase, and the solid product is obtained after purification, wherein the yield is 80%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product. Measured by integrating sphereThe fluorescence quantum yield of compound M6 was 95%.
Example 7
Preparation of non-doped organic light-emitting diode
Indium Tin Oxide (ITO) glass with the square resistance of 15 omega, which is prepared in advance, is taken, and ultrasonic cleaning and plasma treatment are sequentially carried out on the Indium Tin Oxide (ITO) glass for 10 minutes by using acetone, a detergent, deionized water and isopropanol. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN) as a hole injection layer with a thickness of 5nm, 4 '-cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC) as a hole transport layer with a thickness of 25nm, 4' -tris (carbazol-9-yl) triphenylamine (TCTA) as an exciton blocking layer with a thickness of 15nm, a light emitting small molecule containing acridine and phenanthroimidazole with a thickness of 20nm as a light emitting layer, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) as an electron transport layer with a thickness of 40nm, lithium fluoride (LiF) as an electron injection layer with a thickness of 1nm, and a layer, Aluminum (Al) 100nm thick was used as the cathode. The device structure is as follows: ITO/HATCN/TAPC/TCTA/M1-M3/TPBi/LiF/Al. The light-emitting micromolecules containing acridine and phenanthroimidazole are a compound M1, a compound M2 and a compound M3 respectively.
The electroluminescence data of the prepared undoped device are shown in Table 1.
Table 1 organic light emitting device performance based on undoped light emitting layer
From table 1, it can be seen that the OLED devices prepared from these materials all have very low turn-on voltage, high brightness and current efficiency, and according to the color coordinates, these materials all emit pure blue light or deep blue light.
Example 8
Preparation of doped organic light emitting diode
Indium Tin Oxide (ITO) glass with the square resistance of 15 omega, which is prepared in advance, is taken, and ultrasonic cleaning and plasma treatment are sequentially carried out on the Indium Tin Oxide (ITO) glass for 10 minutes by using acetone, a detergent, deionized water and isopropanol. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-Hexaazatriphenylene (HATCN) with the thickness of 5nm as a hole injection layer, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) with the thickness of 40nm as a hole transport layer, 4 '-tris (carbazol-9-yl) triphenylamine (TCTA) with the thickness of 5nm as an exciton blocking layer, 9' - (1, 3-phenyl) di-9H-carbazole (mCP) with the thickness of 20nm and a light-emitting small molecule (10 mass percent) mixed film containing acridine and phenanthroimidazole are sequentially evaporated on the surface of ITO in a vacuum evaporation device to form 1,3 with the thickness of 40nm, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi) as the electron transport layer, lithium fluoride (LiF) 1nm thick as the electron injection layer, and aluminum (Al) 100nm thick as the cathode. The device structure is as follows: ITO/HATCN/NPB/TCTA/mCP M4-M6 (10%)/TPBi/LiF/Al. The light-emitting micromolecules containing acridine and phenanthroimidazole are a compound M4, a compound M5 and a compound M6 respectively.
The electroluminescent spectrum of the small molecule M4 under the doped device structure is shown in FIG. 2, and the emission peak of the device is about 460nm, which is standard blue light emission; the current density-voltage curve of the small molecule M5 under the doped device structure is shown in fig. 3, and it can be seen from fig. 3 that the maximum emission wavelength of M5 under the electric field is about 450nm, the half-peak width of the electroluminescence spectrum is about 65nm, which is typical blue light emission, and it can be found that high current density can be obtained under lower voltage, which indicates that the molecule has higher carrier mobility; the current efficiency-current density curve of the small molecule M6 under the doped device structure is shown in FIG. 4, and it can be found from FIG. 4 that the device current of the small molecule is higher, i.e. the small molecule has higher current efficiency and smaller efficiency roll-off, which indicates that the carrier transport capability is stronger.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (7)
1. A D-A type luminous micromolecule containing acridine and phenanthroimidazole is characterized in that the chemical structural formula of the micromolecule is one of the following structures:
wherein R is H, F, CN or alkyl; r' is methyl or phenyl.
2. The acridine and phenanthroimidazole-containing D-A type light-emitting small molecule according to claim 1, wherein the number of carbon atoms of the alkyl group is 1-4.
3. The use of the acridine and phenanthroimidazole-containing D-A type light-emitting small molecule as claimed in claim 1 in an organic electroluminescent device.
4. The use of acridine and phenanthroimidazole containing D-A type light-emitting small molecules as claimed in claim 3 in organic electroluminescent devices, characterized in that the organic electroluminescent devices comprise light-emitting diode devices.
5. The application of the D-A type light-emitting micromolecules containing acridine and phenanthroimidazole in the organic electroluminescent device according to claim 3, wherein the organic electroluminescent device is in a structure of an anode/a hole injection layer/a hole transport layer/a light-emitting layer/an electron transport layer/an electron injection layer/a cathode.
6. The use of the acridine and phenanthroimidazole-containing D-A type light-emitting small molecule in an organic electroluminescent device according to claim 4, wherein the light-emitting layer contains the acridine and phenanthroimidazole-containing D-A type light-emitting small molecule.
7. The application of the D-A type luminous micromolecules containing acridine and phenanthroimidazole in the organic electroluminescent device as claimed in claim 4, characterized in that the luminous layer is a pure micromolecule film containing the luminous micromolecules of acridine and phenanthroimidazole or a mixed film containing the luminous micromolecules of acridine and phenanthroimidazole and doped host material.
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