CN108164445B - self-host organic light-emitting small molecular material and preparation method and application thereof - Google Patents

self-host organic light-emitting small molecular material and preparation method and application thereof Download PDF

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CN108164445B
CN108164445B CN201810035056.9A CN201810035056A CN108164445B CN 108164445 B CN108164445 B CN 108164445B CN 201810035056 A CN201810035056 A CN 201810035056A CN 108164445 B CN108164445 B CN 108164445B
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CN108164445A (en
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苏仕健
徐志达
高阔
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a self-body organic light-emitting micromolecule material, which is connected with a sulfur-containing non-conjugated unit through carbonyl, and two sides of the self-body organic light-emitting micromolecule material are respectively connected with a benzene ring to increase reaction sites. The invention also discloses a preparation method and application of the self-body organic light-emitting micromolecule material. The self-host organic light-emitting small molecular material realizes intramolecular charge transfer effect, and the sulfur-containing non-conjugated unit of the self-host organic light-emitting small molecular material can serve as a part of host effect, so that high device performance is shown in a simplified device structure. The preparation method of the material is simple, and various target products are obtained through a series of simple reactions. The material of the invention has definite molecular weight, single structure, high decomposition temperature and low sublimation temperature, and is easy to sublimate into the luminescent material with high purity.

Description

Self-host organic light-emitting small molecular material and preparation method and application thereof
Technical Field
The invention relates to the technical field of materials of organic electroluminescent devices, in particular to a self-body organic light-emitting small molecular material and a preparation method and application thereof.
background
organic electroluminescent devices have been currently used in the field of light emitting displays. Compared with polymer luminescent materials, the small-molecule luminescent materials have the advantages of simple preparation, definite molecular weight, single structure and the like, and therefore have more potential to be pushed to wider commercial application. At present, techniques for preparing multilayer devices based on evaporation or solution processing of small molecule materials are constantly being developed and advanced, and have made significant progress.
Significant progress has been made in the current research on organic electroluminescent devices. When the organic light-emitting material is excited by electricity, the theoretical ratio of generated singlet state excitons to generated triplet state excitons is 1: 3. The exciton transition back to the ground state of the singlet level is allowable, and the exciton transition back to the ground state of the triplet level is forbidden, and therefore, the exciton utilization ratio of the general fluorescent material is not high. However, for a material having a small difference between the singlet level and the triplet level, triplet excitons, which have a slightly low energy level and a long lifetime, can be thermally excited to transit to the singlet level through intersystem crossing, and then emit fluorescence, which is called thermally-excited delayed fluorescence. The development of the thermal excitation delayed fluorescence material plays a key role in improving the efficiency of the organic electroluminescent device, can avoid using noble metals of phosphorescent materials, and has positive significance for wider commercial application.
Currently, most of the light-emitting molecules require another material to be added to the light-emitting layer to disperse the light-emitting molecules due to the quenching effect caused by aggregation, thereby reducing the quenching effect. However, after the host-guest light emitting layer system is introduced, the complexity of the device preparation process will be increased. Meanwhile, because the host material generally has poor transmission performance, the turn-on voltage of the device is also increased. Therefore, the organic pure film luminescent layer adopting the non-doping process has unique advantages in the aspects of reducing the cost of the electroluminescent device, improving the performance of the device and the like. It is important to explore the relationship between the molecular structure design and the corresponding performance of the self-host luminescent material which can be efficiently expressed in the device without the need of the host power assistance.
Disclosure of Invention
In order to overcome the above disadvantages and shortcomings of the prior art, the present invention aims to provide a self-host organic light-emitting small molecule material, which is based on carbonyl and sulfur-containing units, has a single material structure, a definite molecular weight, and good solubility and film-forming properties.
The invention also aims to provide a preparation method of the self-host organic light-emitting small molecule material.
The invention also aims to provide application of the self-host organic light-emitting small molecule material.
the purpose of the invention is realized by the following technical scheme:
A self-host organic light-emitting small molecule material has any one of the following chemical structures P1n, P2n, P3n and P4 n:
wherein Ar is any aromatic amine group in the following (1) to (7):
The self-host organic light-emitting small molecule material has any one of the following structures:
A preparation method of a self-host organic light-emitting small molecule material comprises the following steps:
(1) Preparing an intermediate as described in any one of (a) to (d) below:
(2) Under the protection of inert gas, adding the intermediate prepared in the step (1), an aromatic amine compound, alkali and a catalyst into an organic solvent, uniformly mixing, heating, refluxing, stirring and reacting, and carrying out cooling, extraction, spin-drying of the solvent and column chromatography to obtain the novel double-acceptor-unit-based organic micromolecule luminescent material;
the molar ratio of the intermediate to the aromatic amine compound is 1 (2-2.5).
The preparation of any one of the intermediates having the structures (a) to (d) in the step (1) specifically comprises the following steps:
Under the protection of nitrogen, dissolving a raw material of dibromophenylsulfide into anhydrous tetrahydrofuran, cooling to-70 to-80 ℃, sequentially adding N-butyllithium solution and monobromobenzaldehyde, recovering to room temperature, stirring overnight under the atmosphere of N2, and adding ethanol to terminate the reaction after the reaction is finished; extracting, drying, filtering and separating reactants to obtain colorless liquid; oxidizing the colorless liquid by PCC with 5-8 times of molar equivalent, and extracting and separating to obtain a white solid;
The dosage of the n-butyl lithium is 1-1.5 times of the molar weight of the dibromophenylsulfide; the dosage of the monobromobenzaldehyde is 1-1.5 times of the molar weight of the dibromophenylsulfide.
Heating, refluxing and stirring for reaction in the step (2), specifically:
The temperature is 90-110 ℃, and the reaction time is 12-24 h.
The aromatic amine compound in the step (2) is any one of carbazole, 9' -dimethylacridine, phenoxazine or phenothiazine.
the alkali in the step (2) is organic alkali, and the using amount of the alkali is 1.8-2.5 times of the molar equivalent of the aromatic amine compound.
the catalyst in the step (2) consists of palladium acetate and tributyl phosphine.
and (3) the organic solvent in the step (2) is toluene.
the self-host organic light-emitting small molecular material is applied to an electroluminescent diode.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the self-body organic light-emitting micromolecule material simultaneously adopts benzophenone to be connected with the sulfur-containing unit and is connected with the commonly used electron donor unit to obtain a molecule with a D-A structure, has the advantages of single structure, definite molecular weight, good repeatability of multiple synthesis and the like, and is favorable for researching the relationship between the structure and the performance.
(2) the self-host organic light-emitting micromolecule material simultaneously introduces carbonyl and a sulfur-containing unit which are connected through a benzene ring, and the sulfur-containing unit does not participate in the light-emitting process but can be used as a host to disperse the light-emitting unit due to the fact that the sulfur atom can break the conjugation effect of a molecular chain, so that the self-host organic light-emitting micromolecule material can be applied to a pure film light-emitting layer of a non-doped optical device with a simpler process.
(3) the structure of the self-host organic light-emitting micromolecule material can adjust the photoelectric device performances of the material, such as light color, charge transmission performance and the like, by changing the types of the connecting groups.
(4) The structure of the self-host organic light-emitting micromolecule material can adjust and control the conjugation length, the electron cloud distribution, the carrier transmission characteristic and the film forming property of the material by adjusting the connecting position and the number of the groups.
(5) the preparation method of the self-body organic light-emitting micromolecule material is simple to prepare, and various target products are obtained through a series of simple reactions.
(6) the self-body organic light-emitting small molecular material has high decomposition temperature and low sublimation temperature, is easy to sublimate into a high-purity light-emitting material, and can be applied to an organic light-emitting diode.
drawings
FIG. 1 shows the absorption and emission spectra of P18 and P20 in toluene solution.
fig. 2 is a current density-voltage-luminance curve of the organic light emitting diode device including P18, P20.
Fig. 3 is a luminance-current efficiency curve of an organic light emitting diode device including P18, P20.
FIG. 4 is a graph of temperature transition transient lifetime spectra of P18 and P20 in thin films.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
example 1
This example prepared intermediates 1 to 14 and compound P1:
The specific preparation steps of the intermediate 1 are as follows:
In a 250mL three-necked flask, under a nitrogen atmosphere, 11.7g (40.0mmol) of p-bromoiodobenzene, 5.8g (24.0mmol) of sodium sulfide nonahydrate, 336mg (0.1equ) of copper iodide (CuI), 5.4g (40.0mmol) of anhydrous potassium carbonate, and 80mL of N, N-Dimethylformamide (DMF) were successively added. The reaction mixture was heated to 120 ℃ and stirred for 18 hours in the dark. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 7g of intermediate of formula 1 in 94% yield, C12H8Br2S M/Z341.87. m/z 343.87 (100.0%), 341.87 (51.4%), 345.87 (48.6%), 344.87 (9.7%), 346.87 (6.3%), 345.87 (4.5%), 342.87 (4.4%), 344.87 (3.2%), 343.87 (2.3%), 342.87 (2.2%), 347.86 (2.2%); elemental analysis: c, 41.89; h, 2.34; br, 46.45; and S, 9.32.
The specific preparation steps of the intermediate 2 are as follows:
Under a nitrogen atmosphere, in a 250mL three-necked flask, 11.7g (40.0mmol) of m-bromoiodobenzene, 5.8g (24.0mmol) of sodium sulfide nonahydrate, 336mg (0.1equ) of copper iodide (CuI), 5.4g (40.0mmol) of anhydrous potassium carbonate, and 80mL of N, N-Dimethylformamide (DMF) were successively added. The reaction mixture was heated to 120 ℃ and stirred for 18 hours in the dark. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 6.3g of intermediate of formula 1 in 85% yield, C12H8Br2S M/Z341.87. m/s: m/z 343.87 (100.0%), 341.87 (51.4%), 345.87 (48.6%), 344.87 (9.7%), 346.87 (6.3%), 345.87 (4.5%), 342.87 (4.4%), 344.87 (3.2%), 343.87 (2.3%), 342.87 (2.2%), 347.86 (2.2%); elemental analysis: c, 41.89; h, 2.34; br, 46.45; and S, 9.32.
The specific preparation steps of the intermediate 3 are as follows:
5.1g (15mmol) of Compound 1 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of freshly distilled tetrahydrofuran solution in which 2.7g (15mmol) of p-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4.2g of intermediate of formula 3 in 62% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
the specific preparation steps of the intermediate 4 are as follows:
5.1g (15mmol) of Compound 2 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of freshly distilled tetrahydrofuran solution in which 2.7g (15mmol) of p-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4.5g of intermediate of formula 4 in 67% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
The specific preparation steps of the intermediate 5 are as follows:
5.1g (15mmol) of Compound 1 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of a new tetrahydrofuran solution in which 2.7g (15mmol) of M-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under the condition of heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4g of intermediate of formula 5 in 60% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
The specific preparation steps of the intermediate 6 are as follows:
5.1g (15mmol) of Compound 2 was placed in a dry 250mL three-necked flask under a nitrogen atmosphere, and 50mL of freshly distilled tetrahydrofuran was charged. The reactor is cooled to-78 ℃, 6mL of 2.5M n-butyllithium (nBuLi) is added dropwise, the mixture is stirred at low temperature for two hours, 50mL of a new tetrahydrofuran solution in which 2.7g (15mmol) of M-bromobenzaldehyde is dissolved is slowly added, and the mixture is kept under the condition of heat preservation and stirred for one half hour. The reaction was then brought to room temperature and stirred overnight. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 4g of intermediate of formula 6 in 60% yield, C19H14Br2OS M/Z450.19. m/z 449.91 (100.0%), 447.91 (51.4%), 451.91 (48.6%), 450.91 (10.8%), 452.91 (10.0%), 450.91 (9.7%), 448.92 (6.1%), 451.91 (4.5%), 448.92 (4.4%), 449.91 (2.3%), 453.90 (2.2%), 451.92 (1.2%); elemental analysis: c, 50.69; h, 3.13; br, 35.50; o, 3.55; and S, 7.12.
The specific preparation steps of the intermediate 7 are as follows:
in a 250mL single-neck flask, 3.4g (7.6mmol) of Compound 3 was placed, followed by addition of 100mL of methylene chloride and dissolution with stirring, followed by addition of 4.92g (22.8mmol) of pyridinium chlorochromate (PCC) and stirring at room temperature for 8 hours. After the reaction is finished, the solvent in the reaction system is suspended to be dry, dichloromethane and water are used for extraction for three times, and an organic phase is taken. The dichloromethane was distilled off under reduced pressure and purified by silica gel column to give 3.2g of intermediate of formula 9 in 94% yield, C19H12Br2OS M/Z448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15.
The specific preparation steps of the intermediate 8 are as follows:
the reaction step for the preparation of intermediate 7 was changed from compound 3 to compound 4, and the remaining steps were the same as the starting materials, to give intermediate 3.1g of formula 8, yield 91%, C19H12Br2OS M/Z448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15.
The specific preparation steps of the intermediate 9 are as follows:
the reaction step for the preparation of intermediate 7 was changed from compound 3 to compound 5, and the remaining steps were the same as the starting material, to give intermediate 3g of formula 9 in 87% yield, C19H12Br2OS M/Z448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15.
The specific preparation steps of the intermediate 10 are as follows:
the reaction step for the preparation of intermediate 7 was changed from compound 3 to compound 6, and the remaining steps were the same as the starting materials, to give intermediate 3g of formula 10 in 87% yield, C19H12Br2OS M/Z448.17. m/z 447.90 (100.0%), 445.90 (51.4%), 449.89 (48.6%), 448.90 (10.8%), 450.90 (10.0%), 448.90 (9.7%), 446.90 (6.1%), 449.89 (4.5%), 446.90 (4.4%), 447.89 (2.3%), 451.89 (2.2%), 449.90 (1.2%); elemental analysis: c, 50.92; h, 2.70; br, 35.66; o, 3.57; and S, 7.15.
The specific preparation steps of the compound P1 are as follows:
100ml of toluene, 1g of intermediate 10(2.99mmol) and 1.26g of diphenylamine (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.30g of product is obtained, yield 85%. The molecular formula is as follows: C43H32N2 OS; M/Z624.22 theory: M/Z624.22 (100.0%), 625.23 (46.5%), 626.23 (10.6%), 626.22 (4.5%), 627.22 (2.1%); elemental analysis C, 82.66; h, 5.16; n, 4.48; o, 2.56; and S, 5.13.
Example 2
This example prepares compound P2, which has the following structural formula and synthetic route:
The intermediate 10 in example 1 was replaced with an equivalent amount of intermediate 8 and the other starting materials and procedures were the same as in example 1 to give 1.50g of the product of formula P2 in 76% yield. The molecular formula is as follows: C43H32N2 OS; M/Z624.22 theory: M/Z624.22 (100.0%), 625.23 (46.5%), 626.23 (10.6%), 626.22 (4.5%), 627.22 (2.1%); elemental analysis C, 82.66; h, 5.16; n, 4.48; o, 2.56; and S, 5.13.
example 3
This example prepares compound P3, which has the following structural formula and synthetic route:
the equivalent amount of intermediate 9 was substituted for intermediate 10 in example 1 and the other starting materials and procedures were the same as in example 1 to give 1.45g of product of formula P3 in 74% yield. The molecular formula is as follows: C43H32N2 OS; M/Z624.22 theory: M/Z624.22 (100.0%), 625.23 (46.5%), 626.23 (10.6%), 626.22 (4.5%), 627.22 (2.1%); elemental analysis C, 82.66; h, 5.16; n, 4.48; o, 2.56; and S, 5.13.
Example 4
This example prepares compound P4, which has the following structural formula and synthetic route:
The equivalent amount of intermediate 7 was substituted for intermediate 10 in example 1 and the other starting materials and procedures were the same as in example 1 to give 1.45g of the product of formula P4 in 74% yield. The molecular formula is as follows: C43H32N2 OS; M/Z624.22 theory: M/Z624.22 (100.0%), 625.23 (46.5%), 626.23 (10.6%), 626.22 (4.5%), 627.22 (2.1%); elemental analysis C, 82.66; h, 5.16; n, 4.48; o, 2.56; and S, 5.13.
Example 5
This example prepares compound P5, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 10(2.99mmol) and 1.26g of carbazole (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 0.85g of product is obtained, yield 56%. The molecular formula is as follows: C43H28N2 OS; M/Z620.19 theory: M/Z620.19 (100.0%), 621.20 (46.5%), 622.20 (10.6%), 622.19 (4.5%), 623.19 (2.1%); elemental analysis C, 83.20; h, 4.55; n, 4.51; o, 2.58; and S, 5.16.
example 6
this example prepares compound P6, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
The equivalent amount of intermediate 8 was substituted for intermediate 10 in example 5 and the other starting materials and procedures were the same as in example 5 to give 0.80g of the product of formula P6 in 50% yield. The molecular formula is as follows: C43H28N2 OS; M/Z620.19 theory: M/Z620.19 (100.0%), 621.20 (46.5%), 622.20 (10.6%), 622.19 (4.5%), 623.19 (2.1%); elemental analysis C, 83.20; h, 4.55; n, 4.51; o, 2.58; and S, 5.16.
example 7
This example prepares compound P7, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
The equivalent amount of intermediate 9 was substituted for intermediate 10 in example 5 and the other starting materials and procedures were the same as in example 5 to give 0.80g of the product of formula P7 in 50% yield. The molecular formula is as follows: C43H28N2 OS; M/Z620.19 theory: M/Z620.19 (100.0%), 621.20 (46.5%), 622.20 (10.6%), 622.19 (4.5%), 623.19 (2.1%); elemental analysis C, 83.20; h, 4.55; n, 4.51; o, 2.58; and S, 5.16.
example 8
This example prepares compound P8, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
the equivalent amount of intermediate 7 was substituted for intermediate 10 in example 5 and the other starting materials and procedures were the same as in example 5 to give 0.95g of product of formula P8 in 62% yield. The molecular formula is as follows: C43H28N2 OS; M/Z620.19 theory: M/Z620.19 (100.0%), 621.20 (46.5%), 622.20 (10.6%), 622.19 (4.5%), 623.19 (2.1%); elemental analysis C, 83.20; h, 4.55; n, 4.51; o, 2.58; and S, 5.16.
Example 9
this example prepares compound P9, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 10(2.99mmol) and 1.50g of phenothiazine (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tri-tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. The product was obtained in 1.21g with a yield of 63%. The molecular formula is as follows: C43H28N2OS 3; M/Z684.14 theoretical value M/Z684.14 (100.0%), 685.14 (46.5%), 686.13 (13.6%), 686.14 (10.6%), 687.14 (6.3%), 685.14 (2.4%), 688.14 (1.4%), 686.14 (1.1%); elemental analysis C, 75.41; h, 4.12; n, 4.09; o, 2.34; s, 14.04.
Example 10
This example prepares compound P10, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
the equivalent amount of intermediate 8 was substituted for intermediate 10 in example 9 and the other starting materials and procedures were the same as in example 9 to give 1.02g of product of formula P10 in 55% yield. The molecular formula is as follows: C43H28N2OS 3; M/Z684.14 theoretical value M/Z684.14 (100.0%), 685.14 (46.5%), 686.13 (13.6%), 686.14 (10.6%), 687.14 (6.3%), 685.14 (2.4%), 688.14 (1.4%), 686.14 (1.1%); elemental analysis C, 75.41; h, 4.12; n, 4.09; o, 2.34; s, 14.04.
example 11
this example prepares compound P11, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
the equivalent amount of intermediate 9 was substituted for intermediate 10 in example 9 and the other starting materials and procedures were the same as in example 9 to give 0.95g of the product of formula P11 in 50% yield. The molecular formula is as follows: C43H28N2OS 3; M/Z684.14 theoretical value M/Z684.14 (100.0%), 685.14 (46.5%), 686.13 (13.6%), 686.14 (10.6%), 687.14 (6.3%), 685.14 (2.4%), 688.14 (1.4%), 686.14 (1.1%); elemental analysis C, 75.41; h, 4.12; n, 4.09; o, 2.34; s, 14.04.
Example 12
This example prepares compound P12, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 7 were substituted for intermediate 10 in example 9 and the other starting materials and procedures were the same as in example 9 to give 1.21g of product of formula P12 in 61% yield. The molecular formula is as follows: C43H28N2OS 3; M/Z684.14 theoretical value M/Z684.14 (100.0%), 685.14 (46.5%), 686.13 (13.6%), 686.14 (10.6%), 687.14 (6.3%), 685.14 (2.4%), 688.14 (1.4%), 686.14 (1.1%); elemental analysis C, 75.41; h, 4.12; n, 4.09; o, 2.34; s, 14.04.
Example 13
This example prepares compound P13, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 10(2.99mmol) and 1.40g of phenoxazine (2.5equ) were added to a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added with stirring, and the mixture was reacted at 100 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.15g of product are obtained, yield 62%. The molecular formula is as follows: C43H28N2O 3S; M/Z652.18 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
Example 14
This example prepares compound P14, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
Equivalent amounts of intermediate 8 were substituted for intermediate 10 in example 13 and the other starting materials and procedures were the same as in example 13 to give 1.02g of product of formula P14 in 55% yield. The molecular formula is as follows: C43H28N2O 3S; M/Z652.18 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
example 15
This example prepares compound P15, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
the equivalent amount of intermediate 9 was substituted for intermediate 10 in example 13 and the other starting materials and procedures were the same as in example 13 to give 0.95g of product of formula P15 in 50% yield. The molecular formula is as follows: C43H28N2O 3S; M/Z652.18 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
Example 16
this example prepares compound P16, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
Equivalent amounts of intermediate 7 were substituted for intermediate 10 in example 13 and the other starting materials and procedures were the same as in example 13 to give 1.21g of product of formula P16 in 61% yield. The molecular formula is as follows: C43H28N2O 3S; M/Z652.18 theory: M/Z652.18 (100.0%), 653.19 (46.5%), 654.19 (10.6%), 654.18 (4.5%), 655.18 (2.1%); elemental analysis C, 79.12; h, 4.32; n, 4.29; o, 7.35; and S, 4.91.
Example 17
This example prepares compound P17, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 10(2.99mmol) and 1.40g of dimethylacridine (2.5equ) were charged in a three-necked flask under nitrogen atmosphere, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.50g of product is obtained, yield 68%. The molecular formula is as follows: C49H40N2 OS; theoretical value of M/Z704.29 704.29 (100.0%), 705.29 (53.0%), 706.29 (13.8%), 706.28 (4.5%), 707.29 (2.4%), 707.30 (1.5%); elemental analysis C, 83.49; h, 5.72; n, 3.97; o, 2.27; and S, 4.55.
Example 18
This example prepares compound P18, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
The equivalent amount of intermediate 8 was substituted for intermediate 10 in example 17 and the other starting materials and procedures were the same as in example 17 to give 1.22g of product of formula P18 in 55% yield. The molecular formula is as follows: C49H40N2 OS; theoretical value of M/Z704.29 704.29 (100.0%), 705.29 (53.0%), 706.29 (13.8%), 706.28 (4.5%), 707.29 (2.4%), 707.30 (1.5%); elemental analysis C, 83.49; h, 5.72; n, 3.97; o, 2.27; and S, 4.55.
The absorption and emission spectrum of the compound P18 prepared in this example in a toluene solution is shown in FIG. 1, and it can be seen from the figure that the molecule has a very weak CT absorption peak, belongs to a weak CT type molecule, and conforms to the characteristics of a thermally activated delayed fluorescence molecule, and the emission peak of the molecule is 520nm, and belongs to green light emission.
Example 19
this example prepares compound P19, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
The equivalent amount of intermediate 9 was substituted for intermediate 10 in example 17 and the other starting materials and procedures were the same as in example 17 to give 1.18g of product of formula P19 in 50% yield. The molecular formula is as follows: C49H40N2 OS; theoretical value of M/Z704.29 704.29 (100.0%), 705.29 (53.0%), 706.29 (13.8%), 706.28 (4.5%), 707.29 (2.4%), 707.30 (1.5%); elemental analysis C, 83.49; h, 5.72; n, 3.97; o, 2.27; and S, 4.55.
example 20
this example prepares compound P20, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
The equivalent amount of intermediate 7 was substituted for intermediate 10 in example 17 and the other starting materials and procedures were the same as in example 17 to give 1.38g of product of formula P20 in 61% yield. The molecular formula is as follows: C49H40N2 OS; theoretical value of M/Z704.29 704.29 (100.0%), 705.29 (53.0%), 706.29 (13.8%), 706.28 (4.5%), 707.29 (2.4%), 707.30 (1.5%); elemental analysis C, 83.49; h, 5.72; n, 3.97; o, 2.27; and S, 4.55.
The absorption and emission spectrum of the compound P20 prepared in this example in a toluene solution is shown in FIG. 1, and it can be seen from the figure that the molecule has a very weak CT absorption peak, belongs to a weak CT type molecule, and conforms to the characteristics of a thermally activated delayed fluorescence molecule, and the emission peak of the molecule is 520nm, and belongs to green light emission. The emission peak is basically coincident with the P18 compound, which indicates that the adjacent sulfur and phenyl acridine units do not influence the luminescence process of the molecule.
Example 21
this example prepares compound P21, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.26g of 3, 6-tert-butylcarbazole (2.5equ) were charged in a three-necked flask under nitrogen protection, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tri-tert-butylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 0.85g of product is obtained, yield 56%. The molecular formula is as follows: C59H60N2 OS; M/Z844.43 theoretical value M/Z844.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 83.84; h, 7.16; n, 3.31; o, 1.89; s, 3.79.
Example 22
This example prepares compound P22, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
The equivalent of intermediate 10 was substituted for intermediate 14 in example 21 and the other starting materials and procedures were the same as in example 21 to give 0.80g of the product of formula P22 in 50% yield. The molecular formula is as follows: C59H60N2 OS; M/Z844.43 theoretical value M/Z844.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 83.84; h, 7.16; n, 3.31; o, 1.89; s, 3.79.
example 23
This example prepares compound P23, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
the equivalent of intermediate 12 was substituted for intermediate 14 in example 21 and the other starting materials and procedures were the same as in example 21 to give 0.80g of the product of formula P23 in 50% yield. The molecular formula is as follows: C59H60N2 OS; M/Z844.43 theoretical value M/Z844.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 83.84; h, 7.16; n, 3.31; o, 1.89; s, 3.79.
example 24
this example prepares compound P24, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
Equivalent amounts of intermediate 8 were substituted for intermediate 14 in example 21 and the other starting materials and procedures were the same as in example 21 to give 0.95g of product of formula P24 in 62% yield. The molecular formula is as follows: C59H60N2 OS; M/Z844.43 theoretical value M/Z844.43 (100.0%), 877.44 (63.8%), 878.44 (20.0%), 878.43 (4.5%), 879.44 (3.3%), 879.43 (2.9%); elemental analysis C, 83.84; h, 7.16; n, 3.31; o, 1.89; s, 3.79.
Example 25
This example prepares compound P25, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
100ml of toluene, 1g of intermediate 14(2.99mmol) and 1.40g of 3, 6-tert-butyldimethylacridine (2.5equ) were charged in a three-necked flask under nitrogen atmosphere, 0.90g of sodium tert-butoxide and 59.8mg of palladium acetate and tributylphosphine were added under stirring, and the mixture was reacted at 90 ℃ overnight. Cooling, extracting organic phase with dichloromethane, spin drying, and passing through column. 1.50g of product is obtained, yield 68%. The molecular formula is as follows: C65H72N2 OS; theoretical M/Z928.54 value 928.54 (100.0%), 929.54 (70.3%), 930.54 (24.3%), 931.55 (4.7%), 930.53 (4.5%), 931.54 (3.2%), 932.54 (1.1%); elemental analysis C, 84.01; h, 7.81; n, 3.01; o, 1.72; and S, 3.45.
Example 26
This example prepares compound P26, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
equivalent amounts of intermediate 10 were substituted for intermediate 14 in example 25 and the other starting materials and procedures were the same as in example 25 to give 1.22g of product of formula P26 in 55% yield. The molecular formula is as follows: C65H72N2 OS; theoretical M/Z928.54 value 928.54 (100.0%), 929.54 (70.3%), 930.54 (24.3%), 931.55 (4.7%), 930.53 (4.5%), 931.54 (3.2%), 932.54 (1.1%); elemental analysis C, 84.01; h, 7.81; n, 3.01; o, 1.72; and S, 3.45.
Example 27
This example prepares compound P27, which has the following structural formula and synthetic route:
The specific implementation steps are as follows:
equivalent equivalents of intermediate 12 were substituted for intermediate 14 in example 25 and the other starting materials and procedures were the same as in example 25 to give 1.18g of product of formula P27 in 50% yield. The molecular formula is as follows: C65H72N2 OS; theoretical M/Z928.54 value 928.54 (100.0%), 929.54 (70.3%), 930.54 (24.3%), 931.55 (4.7%), 930.53 (4.5%), 931.54 (3.2%), 932.54 (1.1%); elemental analysis C, 84.01; h, 7.81; n, 3.01; o, 1.72; and S, 3.45.
example 28
This example prepares compound P28, which has the following structural formula and synthetic route:
the specific implementation steps are as follows:
equivalent amounts of intermediate 14 were substituted for equivalent amount of intermediate 8 in example 25 and the other starting materials and procedures were the same as in example 25 to give 1.38g of product of formula P28 in 61% yield. The molecular formula is as follows: C65H72N2 OS; theoretical M/Z928.54 value 928.54 (100.0%), 929.54 (70.3%), 930.54 (24.3%), 931.55 (4.7%), 930.53 (4.5%), 931.54 (3.2%), 932.54 (1.1%); elemental analysis C, 84.01; h, 7.81; n, 3.01; o, 1.72; and S, 3.45.
example 29
this example prepares the one-sided comparative compound P29, whose structural formula and synthetic route are shown below:
the intermediate 14 in example 17 was replaced with an equivalent amount of bromobenzophenone and the other starting materials and procedures were the same as in example 17 to give 1.18g of the product of formula P28 in 91% yield. The molecular formula is as follows: C28H23 NO; theoretical value of M/Z389.18 389.18 (100.0%), 390.18 (30.3%), 391.18 (2.7%), 391.18 (1.7%); elemental analysis C, 86.34; h, 5.95; n, 3.60; and O, 4.11.
the following are examples of the use of the compounds of the present invention in Organic Light Emitting Diode (OLED) devices:
example 30
The non-doped general device structure implemented by using the compound of the invention as a luminescent material of an OLED device is as follows:
ITO (95nm)/TAPC (20nm)/Pn (35nm)/TmPyPB (55nm)/LiF (1nm)/Al (100nm), wherein ITO is an anode, TAPC is a hole injection layer, TmPyPB is an electron transport layer, LiF is an electron injection layer, and Al is a cathode.
The structural formula of the used material is as follows:
the device preparation process is as follows: carrying out ultrasonic treatment on the ITO transparent conductive glass in a cleaning agent, and then cleaning the ITO transparent conductive glass by deionized water, wherein the ultrasonic treatment is carried out in the presence of acetone: ultrasonic degreasing in mixed solvent of ethanol, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding with low-energy cations.
The glass with the anode ITO is placed in a vacuum chamber and is vacuumized to 1 multiplied by 10-5～9×10-3Pa on the anode filmThe organic material layer is evaporated at a deposition rate, wherein the luminescent material layer is respectively placed on an evaporation source in evaporation of the luminescent layer, and the thickness of the film is controlled by a certain deposition rate and then is evaporatedEvaporating LiF at a deposition rate ofthe Al electrode was evaporated at the deposition rate of (3) to obtain the organic light emitting diode device of the present example.
the current density-voltage-luminance graph and the current efficiency-luminance relationship graph of the organic light emitting diode device of the present embodiment are shown in fig. 2 to 3, and the basic characterization data are shown in table 1.
The temperature-varying transient lifetime spectra of P18 and P20 in the thin film of this example are shown in fig. 4, and the long-life components in the transient spectra increase with increasing temperature, indicating that the long-life components of the molecules have the property of thermal activation, demonstrating that such molecules are molecules with the property of thermal activation delayed fluorescence.
Table 1 test results of OLED devices fabricated
description of the drawings: the devices are non-doped devices with no host molecules doped in the luminescent layer, the preparation process of the devices is simpler than that of the devices using a luminescent layer host-guest system, and the maximum external quantum efficiency of the devices is more than 10%. Particularly, for the device of example 38 based on the P20 material, the maximum external quantum efficiency reaches 17.2%, and the roll-off control of the efficiency of the device is excellent, and the device can meet the practical use requirement at 10000cd/m2the external quantum efficiency of 14% or more is maintained at the luminance of (2). The material has a great application prospect in the aspect of preparing simple, efficient and stable electroluminescent devices.
Compared with the luminescent small molecule P29 without modification of a non-conjugated unit, the independent small molecules P18 and P20 of phenylacridine connected by aryl sulfur show obviously higher highest external quantum efficiency and current efficiency and lower starting voltage under the same non-doped device structure, and the device performance is obviously improved, so that the self-body small molecules can inhibit the quenching effect caused by tight accumulation among molecules to a certain extent in the non-doped device, and the characteristics and advantages of the self-body are fully embodied.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (9)

1. a self-host organic light-emitting small molecule material is characterized by having any one of the following chemical structures P1n, P2n, P3n and P4 n:
Wherein Ar is any aromatic amine group in the following (1) to (7):
2. The self-host organic light-emitting small molecule material of claim 1, having any one of the following structures:
3. A method for preparing a self-host organic light-emitting small molecule material as claimed in claim 1 or 2, comprising the steps of:
(1) Preparing an intermediate as described in any one of (a) to (d) below:
the method for preparing the intermediate of any one of (a) to (d) comprises the following steps: under the protection of nitrogen, dissolving the raw material dibromophenylsulfide into anhydrous tetrahydrofuran, cooling to-70-80 ℃, sequentially adding N-butyllithium solution and monobromobenzaldehyde, recovering to room temperature, and then adding N2stirring overnight under the atmosphere, and adding ethanol to terminate the reaction after the reaction is finished; extracting, drying, filtering and separating reactants to obtain colorless liquid; oxidizing the colorless liquid by PCC with 5-8 times of molar equivalent, and extracting and separating to obtain a white solid;
The dosage of the n-butyl lithium is 1-1.5 times of the molar weight of the dibromophenylsulfide; the dosage of the monobromobenzaldehyde is 1-1.5 times of the molar weight of the dibromophenylsulfide;
(2) under the protection of inert gas, adding the intermediate prepared in the step (1), an aromatic amine compound, alkali and a catalyst into an organic solvent, uniformly mixing, heating, refluxing, stirring and reacting, and obtaining the self-body organic light-emitting micromolecule material through cooling, extraction, spin-drying the solvent and column chromatography;
The molar ratio of the intermediate to the aromatic amine compound is 1 (2-2.5).
4. The method for preparing a self-host organic light-emitting small molecule material according to claim 3, wherein the heating, refluxing and stirring reaction in the step (2) is specifically:
The temperature is 90-110 ℃, and the reaction time is 12-24 h.
5. The method for preparing a self-host organic light-emitting small molecule material according to claim 3, wherein the aromatic amine compound in the step (2) is any one of carbazole, 9' -dimethylacridine, phenoxazine or phenothiazine.
6. The method according to claim 3, wherein the base in step (2) is an organic base, and the amount of the base is 1.8-2.5 times the molar equivalent of the aromatic amine compound.
7. the method for preparing a self-host organic light-emitting small molecule material according to claim 3, wherein the catalyst in the step (2) is composed of palladium acetate and tributyl phosphine.
8. The method for preparing a self-host organic light-emitting small molecule material according to claim 3, wherein the organic solvent in the step (2) is toluene.
9. use of the self-host organic light-emitting small molecule material of any one of claims 1-2 in an electroluminescent diode.
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