WO2020082656A1 - Thermally activated delayed fluorescence monomolecular white light material and synthesizing method therefor, and organic electroluminescent device - Google Patents

Thermally activated delayed fluorescence monomolecular white light material and synthesizing method therefor, and organic electroluminescent device Download PDF

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WO2020082656A1
WO2020082656A1 PCT/CN2019/076409 CN2019076409W WO2020082656A1 WO 2020082656 A1 WO2020082656 A1 WO 2020082656A1 CN 2019076409 W CN2019076409 W CN 2019076409W WO 2020082656 A1 WO2020082656 A1 WO 2020082656A1
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mixed solution
white light
thermally activated
activated delayed
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PCT/CN2019/076409
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Chinese (zh)
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罗佳佳
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武汉华星光电半导体显示技术有限公司
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Priority to US16/333,270 priority Critical patent/US11220627B2/en
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    • C—CHEMISTRY; METALLURGY
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    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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    • C09K2211/1025—Heterocyclic compounds characterised by ligands
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    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the invention relates to the technical field of organic optoelectronic materials, in particular to a thermally activated delayed fluorescent single-molecule white light material, a synthesis method thereof, and an organic electroluminescent device.
  • Photoelectric conversion efficiency is one of the important parameters for evaluating OLEDs. Since the advent of organic light-emitting diodes, various luminescent material systems based on fluorescence and phosphorescence have been developed to improve the luminous efficiency of organic light-emitting diodes. OLEDs based on fluorescent materials have the characteristics of high stability, but are limited by the laws of quantum statistics. Under the action of electrical activation, the ratio of single excited excitons and triplet excited excitons is 1: 3, so fluorescence The internal electroluminescence quantum efficiency of the material is limited to 25%. Phosphorescent materials can use singlet excited state excitons and triplet excited state excitons at the same time due to the heavy atom's orbital coupling. The theoretical quantum efficiency of electron emission can reach 100%. However, OLED materials based on phosphorescence mostly use precious metals, one is high cost, and the other is not environmentally friendly.
  • the luminescent layer plays a leading role, and the performance of the luminescent material is a key factor in determining the performance of the device.
  • the host and guest of the light-emitting layer adopt simple physical doping, inevitable phase separation occurs, and charge transfer complexes and exciplexes are easily formed, which affects the performance of the device.
  • the white light-emitting polymer light-emitting material is a light-emitting system formed by a main chain as a main body and side-chains connecting light-emitting objects of different wavelengths, which can effectively avoid phase separation.
  • the molecular structure of the polymer is uncertain, the repeatability of its synthesis is poor, and the luminous efficiency is not high, which greatly limits its application.
  • the technical problem to be solved by the present invention is to provide a thermally activated delayed fluorescent single-molecule white light material and its synthesis method, organic electroluminescent device, which can effectively solve the uncertainty of the molecular structure of the polymer, the poor repeatability of its synthesis, and luminescence Inefficiency is not a problem.
  • the present invention provides a thermally activated delayed fluorescent single-molecule white light material.
  • the present invention conducts an in-depth study on the currently researched hot thermally activated delayed fluorescent materials, and designs and synthesizes molecular systems with D1-A-D2 structures with different donors.
  • Thermally activated delayed fluorescence monomolecular white light material consists of the raw material of the first group and the raw material of the second group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4
  • the thermally activated delayed fluorescent monomolecular white light material synthesized by the 5-average four wells has the general structural formula:
  • D1 is a first group
  • D2 is the second group
  • the first group and the second group are asymmetric groups.
  • the raw materials of the first group and the second group are each selected from 9,9′-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3, One of 6-dimethylcarbazole, phenothiazine, or acridinone.
  • the present invention also provides a thermally activated delayed fluorescent single-molecule white light material synthesis method, which includes the following steps: a first mixed solution preparation step, the first group of The raw materials and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-both wells and catalyst are placed in the reaction vessel to fully react to obtain the first mixture Solution, the first mixed solution includes the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four well reaction The resulting intermediate; the first extraction step, cooling the first mixed solution to room temperature, extracting the mixed solution and obtaining the intermediate; the second mixed solution preparation step, the raw material of the second group and the The intermediate and the catalyst are placed in the reaction vessel to obtain a second mixed mixed solution, which includes the raw materials of the intermediate and the second group; a second extraction step, the second mixed solution Cool to room temperature, extract the mixed solution
  • the raw materials of the first group and the second group are each selected from 9,9′-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, One of 3,6-dimethylcarbazole, phenothiazine, or acridinone.
  • the molar ratio of the raw material of the first group to 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-metsutsui is 1: 1 ⁇ 1 : 5
  • the molar ratio of the raw material of the second group to the intermediate is 1: 1 to 1: 5.
  • the reaction time is 24 hours and the reaction temperature is 100 ° C; in the second mixed solution preparation step, the reaction time is 24 hours and the reaction temperature is 100 ° C.
  • the catalyst is palladium acetate, tri-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide and toluene.
  • the raw materials of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2, 4,5-Four Sijing, the palladium acetate and the tri-tert-butylphosphine tetrafluoroborate are placed together in the reaction vessel, and then the reaction vessel is placed in an argon atmosphere
  • the sodium tert-butoxide and toluene for removing water and oxygen are added to the reaction vessel to obtain a first reaction solution.
  • the intermediate, the raw material of the second group, palladium acetate and tri-tert-butylphosphine tetrafluoroborate are placed together in the reaction vessel, Then, the reaction container is placed in an argon atmosphere, and the sodium tert-butoxide and toluene in which water and oxygen are removed are added to the reaction container to obtain a second reaction liquid.
  • the first extraction step includes pouring the first mixed solution into ice water, and extracting three times with dichloromethane, and combining the organic phases to obtain the thermally activated delayed fluorescent single molecule white light material;
  • the second extraction step also includes The second mixed solution was poured into ice water, and extracted three times with dichloromethane, and the organic phases were combined to obtain the thermally activated delayed fluorescent single molecule white light material.
  • the invention also provides an organic electroluminescent device, which includes a light-emitting layer, and the luminescent dye of the light-emitting layer is the thermally activated delayed fluorescent monomolecular white light material.
  • the thermally activated delayed fluorescent single-molecule white light material of the present invention is designed to synthesize a molecular system of D1-A-D2 structure with different groups, and arrange and combine D1 and D2 so that the D1-A-D2 structure forms an asymmetric structure. Has a high white light emitting performance.
  • the synthesized thermally activated delayed fluorescent single molecule white light material accounts for a relatively high proportion, effectively improving the synthesis rate of the thermally activated delayed fluorescent single molecule white light material , So that the thermally activated delayed fluorescent single molecule white light material synthesized by this method has higher white light emitting performance.
  • the organic electroluminescent device of the invention adopts the thermally activated delayed fluorescent single molecule white light material prepared by the invention, which has high luminous efficiency and long service life.
  • FIG. 1 is a photoluminescence spectrum chart of the target compound in Example 1.
  • FIG. 1 is a photoluminescence spectrum chart of the target compound in Example 1.
  • FIG. 2 is a transient spectrum chart of the target compound in Example 1.
  • FIG. 2 is a transient spectrum chart of the target compound in Example 1.
  • FIG. 3 is a cross-sectional view of the structure of an organic light emitting telephone of Application Example 1.
  • first and second are used for description purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features.
  • the features defined as “first” and “second” may explicitly or implicitly include one or more of the features.
  • the meaning of “plurality” is two or more, unless otherwise specifically limited.
  • connection should be understood in a broad sense, for example, it can be fixed connection or detachable Connected, or integrally connected; it can be mechanical, electrical, or can communicate with each other; it can be directly connected, or it can be indirectly connected through an intermediary, it can be the connection between two elements or the interaction of two elements relationship.
  • the first feature “above” or “below” the second feature may include the first and second features in direct contact, or may include the first and second features Contact not directly but through other features between them.
  • the first feature is “above”, “above” and “above” the second feature includes that the first feature is directly above and obliquely above the second feature, or simply means that the first feature is higher in level than the second feature.
  • the first feature is “below”, “below” and “below” the second feature includes that the first feature is directly below and obliquely below the second feature, or simply means that the first feature is less horizontal than the second feature.
  • the present invention proposes a class of thermally activated delayed fluorescent single-molecule white light materials.
  • the present invention conducts in-depth research on the currently hot TADF materials, and designs and synthesizes molecular systems with different donors D1-A-D2 structures. Synthesized from the raw material of the first group and the raw material of the second group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-metsutsui Thermally activated delayed fluorescent single molecule white light material, its structural formula is:
  • D1 is a first group
  • D2 is the second group
  • the first group and the second group are asymmetric groups.
  • the raw materials of the first group and the second group are each selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3, One of 6-dimethylcarbazole, phenothiazine, or acridinone.
  • the molecular structure of the first group and the second group is any one of the following, and the first group and the second group are different.
  • the structural formula of the fluorescent single-molecule white light material finally generated may correspond to one of formula (1) -formula (9):
  • thermally activated delayed fluorescent monomolecular white light material in the present invention, the following will be specifically described by method examples 1-3.
  • the first mixed solution preparation step the raw material of the first group and the 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells and catalyst Placed in a reaction vessel to perform a sufficient reaction to obtain a first mixed solution including the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -Intermediate produced by the reaction of 1, 2, 4, 4 and 5 wells.
  • the raw materials of the first group are all selected from 9,9'-diphenylsilaccridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phen One of thiazine or acridinone, preferably 3,6-dimethylcarbazole, the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl
  • the molar ratio of the base-1,2,4,5-averaged four wells is 1: 1, and in other embodiments may be 1: 3, 1: 4, 1: 5.
  • the order of putting the reactants is as follows, the raw material of the first group (1.95g, 10mmol) and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -1,2,4,5-All four wells (4.5g, 10mmol), palladium acetate (90mg, 0.4mmol) and the tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were placed together In the reaction vessel, place the reaction vessel in an argon atmosphere, and add the sodium tert-butoxide NaOt-Bu (1.16g, 12mmol) and 60ml of dehydrated and deoxygenated toluene to the reaction vessel And react at 110 ° C for 24 hours to obtain a reaction solution.
  • the raw material of the first group (1.95g, 10mmol) and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -1,2,4,5-All four wells (4.5
  • First extraction step cooling the first mixed solution to room temperature, extracting the mixed solution and obtaining the intermediate.
  • the first mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was firstly purified using a silica gel column chromatography method to obtain the initial purified product.
  • the volume ratio of the dichloromethane to the n-hexane is 1: 5, and the final separation and purification gives 3.37 g of light blue powder with a yield of 60%.
  • the light blue powder produced is analyzed by the detection equipment according to the detection requirements.
  • the second mixed solution preparation step placing the raw material of the second group, the intermediate and the catalyst in a reaction vessel to obtain a second mixed solution, the second mixed solution including the intermediate and the second group
  • the raw material of the group are all selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole , One of phenothiazine or acridinone, preferably phenothiazine, the raw material of the second group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,
  • the molar ratio of 2,4,5-averaged four wells is 1: 1, in other embodiments it can be 1: 3, 1: 4, 1: 5.
  • the order of putting the reactants is as follows, the intermediate (1.0 g, 5 mmol) and the second group (2.8 g, 5 mmol), palladium acetate (45 mg, 0.2 mmol) and the tri-tert-butyl Phosphine tetrafluoroborate (0.17g, 0.6mmol) was placed in the reaction vessel together, the reaction vessel was placed in an argon atmosphere, and the sodium tert-butoxide was added to the reaction vessel NaOt-Bu (0.58 g, 6 mmol) and 60 ml of toluene dehydrated and deoxygenated were reacted at 110 ° C. for 24 hours to obtain a reaction solution.
  • Second extraction step cooling the second mixed solution to room temperature, extracting the mixed solution and obtaining the target compound, and separating and purifying the target compound to obtain a thermally activated delayed fluorescence single molecule white light material.
  • the second mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was initially purified using a silica gel column chromatography method to obtain the target compound.
  • the volume ratio of the dichloromethane to the n-hexane was 1: 5, and the final separation and purification gave a white powder of 1.7 g with a yield of 50%.
  • the following analysis is performed on the prepared white powder according to the detection requirements by the detection equipment.
  • the first mixed solution preparation step is to combine the raw materials of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells and catalyst Placed in a reaction vessel to perform a sufficient reaction to obtain a first mixed solution including the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -Intermediate produced by the reaction of 1, 2, 4, 4 and 5 wells.
  • the raw materials of the first group are all selected from 9,9'-diphenylsilaccridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phen One of thiazine or acridinone, preferably 9,9'-diphenylsilicoacridine, the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5' -The molar ratio of tetramethyl-1,2,4,5-meat tetrahedron is 1: 1, and in other embodiments may be 1: 3, 1: 4, 1: 5.
  • the order of putting the reactants in the preparation step of the first mixed solution is as follows.
  • the raw materials of the first group (3.5g, 10mmol) and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl- 1,2,4,5-All four wells (4.5g, 10mmol), palladium acetate (90mg, 0.4mmol) and the tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were placed together in the In the reaction vessel, place the reaction vessel in an argon atmosphere, and add the sodium tert-butoxide NaOt-Bu (1.16 g, 12 mmol) and 60 ml of dehydrated and deoxygenated toluene to the reaction vessel.
  • the reaction liquid was obtained by reacting at 110 ° C for 24 hours.
  • the first mixed solution was cooled to room temperature, the mixed solution was extracted and an intermediate was obtained; in the first extraction step, the first mixed solution was poured into 200 mL of ice water and extracted with dichloromethane Three times, the silica gel column chromatography method was used for the first time to purify the target compound to obtain the target compound. During the silica gel column chromatography method, the volume ratio of the dichloromethane to the n-hexane was 1: 5. Isolation and purification gave 3.6 g of light blue powder with a yield of 50%. The following analysis is performed on the prepared white powder according to the detection requirements by the detection equipment.
  • the mass spectrometry result is: MS (EI) m / z: [M] + calcd (theoretical value) for C42H34BrN5Si, 445.97; found (actual value), 446.00.
  • the raw material of the second group, the intermediate, and the catalyst are placed in a reaction vessel to obtain a second mixed solution, and the second mixed solution includes the intermediate and the second group
  • the raw materials of the group; the raw materials of the second group are selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethyl One of carbazole, phenothiazine, or acridinone, preferably iminostilbene, the raw material of the first group, and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-
  • the molar ratio of 1,2,4,5-averaged four wells is 1: 1, in other embodiments it can be 1: 3, 1: 4, 1: 5.
  • the order of putting the reactants is as follows, intermediate 2 (2.86 g, 4 mmol), raw material of the second group (0.77 g, 4 mmol), palladium acetate (38 mg, 0.17 mmol) and Tri-tert-butylphosphine tetrafluoroborate (0.14g, 0.5mmol), placed together in the reaction vessel, then placed the reaction vessel in an argon atmosphere, and added the reaction vessel to the reaction vessel Sodium tert-butoxide NaOt-Bu (0.48 g, 5 mmol) and 60 ml of toluene dehydrated and deoxygenated were reacted at 110 ° C. for 24 hours to obtain a reaction solution.
  • the second mixed solution is cooled to room temperature, the mixed solution is extracted and a target compound is obtained, and the target compound is separated and purified to obtain a thermally activated delayed fluorescence single molecule white light material.
  • the second mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was initially purified using a silica gel column chromatography method to obtain the target compound.
  • the volume ratio of the dichloromethane to the n-hexane was 1: 5, and finally the white powder was separated and purified to obtain 1.2 g, with a yield of 36%.
  • the following analysis is performed on the prepared white powder according to the detection requirements by the detection equipment.
  • the analysis results are: the results of nuclear magnetic hydrogen spectrum and carbon spectrum are: 1H NMR (300MHz, CD2Cl2, ⁇ ): 7.52-7.46 (m, 12H), 7.34 (s, 2H), 7.31 (s, 2H), 7.29-7.23 (m, 4H), 7.19-7.03 (m, 10H), 6.99 (s, 2H), 2.57 (s, 12H).
  • Mass spectrometry results are: MS (EI) m / z: [M] + calcd (theoretical value) for C56H44N6Si, 828.34; found (actual value), 828.30.
  • the elemental analysis results are: Calcd (theoretical value) for C56H44N6Si: C 81.23, H 5.35, N 10.14; found (actual value): C 81.21, H 5.34, N 10.09.
  • the first mixed solution preparation step is to combine the raw materials of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells and catalyst Placed in a reaction vessel to perform a sufficient reaction to obtain a first mixed solution including the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -Intermediate produced by the reaction of 1, 2, 4, 4 and 5 wells.
  • the raw materials of the first group are all selected from 9,9'-diphenylsilaccridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phen One of thiazine or acridinone, preferably 3,6-dimethyl-spirosilane acridine, the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5' -The molar ratio of tetramethyl-1,2,4,5-meat tetrahedron is 1: 1, and in other embodiments may be 1: 3, 1: 4, 1: 5.
  • the order of putting the reactants is as follows, 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells (4.5g, 10mmol), 3,6-dimethyl-spirosilane acridine (3.75g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2 mmol), placed together in the reaction vessel, then placed the reaction vessel in an argon atmosphere, and added the sodium tert-butoxide NaOt-Bu (1.16 g, 12 mmol) and 60 ml to the reaction vessel Toluene which was dehydrated and deoxygenated was reacted at 110 ° C for 24 hours to obtain a first mixed solution.
  • the first mixed solution was cooled to room temperature, the first mixed solution was extracted and an intermediate was obtained; in the first extraction step, the first mixed solution was poured into 200 mL of ice water and extracted three times with dichloromethane , Using a silica gel column chromatography method for the first purification of the target compound to obtain the target compound, in the process of the silica gel column chromatography method, the volume ratio of the dichloromethane and the n-hexane is 1: 5, the final separation Purified to give light blue powder 4.0g, yield 54%.
  • the raw material of the second group, the intermediate, and the catalyst are placed in a reaction vessel to obtain a second mixed solution, and the second mixed solution includes the intermediate and the second group
  • the raw materials of the group; the raw materials of the second group are selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethyl
  • the molar ratio of 1,2,4,5-averaged four wells is 1: 1, in other embodiments it can be 1: 3, 1: 4, 1: 5.
  • the order of putting the reactants is as follows, intermediate 3 (3.7g, 5mmol), acridinone (1.0g, 5mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine Tetrafluoroborate (0.17g, 0.6mmol), then add NaOt-Bu (0.58g, 6mmol) to the glove box, place them together in the reaction vessel, and then place the reaction vessel in an argon atmosphere To the reaction vessel, the sodium tert-butoxide NaOt-Bu (0.58g, 6mmol) and 60ml of dehydrated and deoxygenated toluene were added and reacted at 110 ° C for 24 hours to obtain a reaction solution.
  • the second mixed solution is cooled to room temperature, the mixed solution is extracted and a target compound is obtained, and the target compound is separated and purified to obtain a thermally activated delayed fluorescence single molecule white light material.
  • the second mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was firstly purified using a silica gel column chromatography method to obtain the target compound.
  • the silica gel column chromatography method During the process, the volume ratio of the dichloromethane to the n-hexane was 1: 5, and the final separation and purification gave 1.1 g of white powder with a yield of 26%.
  • the obtained white powder is analyzed according to the detection requirements by the detection equipment.
  • Mass spectrometry results are: MS (EI) m / z: [M] + calcd (theoretical value) for C57H44N6OSi, 856.33; found (actual value) 0,856.23.
  • the elemental analysis result is Calcd (theoretical value) for C57H44N6OSi: C 79.88, H 5.17, N 9.81; found (actual value): C79.83, H 5.14, N 9.69.
  • thermally activated delayed fluorescent monomolecular white light materials as shown in formula (2), formula (9), etc., for the preparation method, see method example 1 to method example 3, the main preparation steps are the same, the only difference is The raw materials of the first group and the second group are different, so they will not be described one by one.
  • the thermally activated delayed fluorescent single-molecule white light material disclosed in the present invention can be applied to organic electroluminescent devices, and is specifically applied to a light-emitting layer.
  • Monomolecular white light materials are considered to be the most promising white light illumination materials due to their excellent light-emitting performance and no phase separation.
  • the present invention conducts in-depth research on the currently hot TADF materials, designs and synthesizes molecular systems of D1-A-D2 structures with different donors, arranges and combines D1 and D2, and selects molecules with excellent white light emitting properties.
  • a general display device includes an organic electroluminescent device, and the light-emitting layer is permanently located in the organic electroluminescent device.
  • an organic electroluminescent device is used for the application of the present invention. Further explanation.
  • the excellent performance of the target compound 1 can be applied to the organic light-emitting device 10.
  • the organic electroluminescent device 10 includes a substrate layer 11, a first functional layer 12, a light-emitting layer 13, a second functional layer 14, and a cathode layer 15;
  • the substrate layer 11 is conductive glass;
  • the first functional layer 12 is a hole transport layer and is attached to the side of the substrate 11;
  • the light-emitting layer 13 is attached to the side of the first functional layer 12 away from the substrate 11;
  • the second functional layer 14 is an electron transport layer and is attached The side of the light-emitting layer 13 away from the first functional layer 12;
  • the cathode layer 15 is attached to the side of the second functional layer 14 away from the light-emitting layer 13.
  • the material of the substrate 1 may be glass and / or conductive glass (ITO), the thickness of which is generally 45-55 nm, and the material of the hole transport and injection layer may be poly 3,4-ethylenedioxythiophene, Polystyrene sulfonate and PEDOT: PSS, the thickness of which is generally 45-55nm; the material of the electron transport layer may be 1,3,5-tris (3- (3-pyridyl) phenyl ) Benzene / TmPyPB, whose thickness is generally 35-45nm; the material of the cathode layer may be lithium fluoride / aluminum, and its thickness is generally 95-105nm.
  • ITO conductive glass
  • the material of the hole transport and injection layer may be poly 3,4-ethylenedioxythiophene, Polystyrene sulfonate and PEDOT: PSS, the thickness of which is generally 45-55nm
  • the material of the electron transport layer may be 1,3,5-tris (3
  • the light-emitting layer 13 uses the thermally activated delayed fluorescent monomolecular white light material (40 nm) of the present invention as the material of the light-emitting layer, and the monomolecular white light material is vapor-deposited at a time under high vacuum conditions.
  • the performance of the electroluminescent device of the present invention is measured, wherein the current-luminance-voltage characteristic of the organic electroluminescent device is The diode's Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) was completed, and the electroluminescence spectrum was measured by the French JY company SPEX CCD3000 spectrometer, all measurements were completed in the room temperature atmosphere.
  • the performance data of the device is shown in Table 1 below:
  • Table 1 shows the performance parameters of the organic electroluminescent device such as the highest brightness and starting voltage.
  • Device 1 is an organic electroluminescent device of the present invention
  • Device 2 is a comparative device
  • the spectral CIE coordinates of Device 1 and Device 2 are both white light. It can be seen that the device 1 provided by the present invention has a higher maximum brightness. Compared with the comparison device 2, the light emitting brightness is improved, and the quantum efficiency is also improved.

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Abstract

The prevent invention provides a macromolecule Thermally Activated Delayed Fluorescence (TADF) material, and further provides a TADF monomolecular white light material, which is synthesized from raw materials of first groups and second groups, and 3,3'-dibromo-1,5,1',5'-tetramethyl-1,2,4,5-tetrahydrazine. The synthesizing method for the TADF monomolecular white light material comprises: a step of preparation of a first mixed solution, a first extraction step, a step of preparation of a second mixed solution, and a second extraction step. An organic electroluminescent device, comprising a TADF monomolecular white light material light-emitting layer.

Description

热活化延迟荧光单分子白光材料及其合成方法、有机电致发光器件Thermally activated delayed fluorescent single molecule white light material and its synthesis method, organic electroluminescent device 技术领域Technical field
本发明涉及有机光电材料技术领域，特别是一种热活化延迟荧光单分子白光材料及其合成方法、有机电致发光器件。The invention relates to the technical field of organic optoelectronic materials, in particular to a thermally activated delayed fluorescent single-molecule white light material, a synthesis method thereof, and an organic electroluminescent device.
背景技术Background technique
光电转换效率是评估OLED的重要参数之一，自有机发光二极管问世以来，为提高有机发光二极管的发光效率，各种基于荧光、磷光的发光材料体系被开发出来。基于荧光材料的OLED具有稳定性高的特点，但受限于量子统计学定律，在电激活作用下，产生的单重激发态激子和三重激发态激子的比例为1:3，因此荧光材料的内部电致发光量子效率被限制在25％。磷光材料由于具有重原子的旋轨耦合作用，可同时利用单重激发态激子和三重激发态激子，其理论内电子发光量子效率能够达到100％。但基于磷光的OLED材料多采用贵重金属，一是成本高，二是不环保。Photoelectric conversion efficiency is one of the important parameters for evaluating OLEDs. Since the advent of organic light-emitting diodes, various luminescent material systems based on fluorescence and phosphorescence have been developed to improve the luminous efficiency of organic light-emitting diodes. OLEDs based on fluorescent materials have the characteristics of high stability, but are limited by the laws of quantum statistics. Under the action of electrical activation, the ratio of single excited excitons and triplet excited excitons is 1: 3, so fluorescence The internal electroluminescence quantum efficiency of the material is limited to 25%. Phosphorescent materials can use singlet excited state excitons and triplet excited state excitons at the same time due to the heavy atom's orbital coupling. The theoretical quantum efficiency of electron emission can reach 100%. However, OLED materials based on phosphorescence mostly use precious metals, one is high cost, and the other is not environmentally friendly.
目前大部分研究都集中在蒸镀型材料，这会使得器件的制作成本变得很高。高分子热活化延迟荧光材料由于良好的成膜性，在湿法加工方面具有明显的优势。但是如何使得热活化延迟荧光高分子保持高的光致发光量子产率以及较大的反向系间窜越常数仍然没有得到解决，这也是目前高分子热活化延迟荧光材料制备的器件外量子效率比较低的原因。Most of the current research is focused on evaporation-type materials, which will make the manufacturing cost of the device very high. Polymer thermally activated delayed fluorescent materials have obvious advantages in wet processing due to their good film-forming properties. However, how to maintain the high photoluminescence quantum yield of the thermally activated delayed fluorescent polymer and the large reverse intersystem crossing constant is still not solved, which is also the external quantum efficiency of the device prepared by the polymer thermally activated delayed fluorescent material The reason is relatively low.
在有机电致发光器件中，起主导作用的为发光层，发光材料的性能是决定器件性能的关键因素。对于传统的小分子白光掺杂器件，其发光层的主客体采用简单的物理掺杂，不可避免的会存在相分离，且容易形成电荷转移复合物以及激基复合物，进而影响器件的性能。白光聚合物发光材料是以主链作为主体，侧链连接不同波长的发光客体的方式形成的发光体系，能够有效地避免相分离。但是，聚合物的分子结构不确定，其合成的重复性差，发光效率低下也不高，极大的限制了它的应用。In organic electroluminescent devices, the luminescent layer plays a leading role, and the performance of the luminescent material is a key factor in determining the performance of the device. For traditional small-molecule white light doped devices, the host and guest of the light-emitting layer adopt simple physical doping, inevitable phase separation occurs, and charge transfer complexes and exciplexes are easily formed, which affects the performance of the device. The white light-emitting polymer light-emitting material is a light-emitting system formed by a main chain as a main body and side-chains connecting light-emitting objects of different wavelengths, which can effectively avoid phase separation. However, the molecular structure of the polymer is uncertain, the repeatability of its synthesis is poor, and the luminous efficiency is not high, which greatly limits its application.
技术问题technical problem
本发明所要解决的技术问题是，提供一种热活化延迟荧光单分子白光材料及其合成方法、有机电致发光器件，可以有效解决了聚合物的分子结构不确定、其合成的重复性差、发光效率低下也不高的问题。The technical problem to be solved by the present invention is to provide a thermally activated delayed fluorescent single-molecule white light material and its synthesis method, organic electroluminescent device, which can effectively solve the uncertainty of the molecular structure of the polymer, the poor repeatability of its synthesis, and luminescence Inefficiency is not a problem.
技术解决方案Technical solution
本发明提供一种热活化延迟荧光单分子白光材料，本发明对目前研究火热的热活化延迟荧光材进行深入研究，设计合成具有不同给体的D1-A-D2结构的分子体系。热活化延迟荧光单分子白光材料由第一基团的原料和第二基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井合成的热活化延迟荧光单分子白光材料，其结构通式为：The present invention provides a thermally activated delayed fluorescent single-molecule white light material. The present invention conducts an in-depth study on the currently researched hot thermally activated delayed fluorescent materials, and designs and synthesizes molecular systems with D1-A-D2 structures with different donors. Thermally activated delayed fluorescence monomolecular white light material consists of the raw material of the first group and the raw material of the second group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4 The thermally activated delayed fluorescent monomolecular white light material synthesized by the 5-average four wells has the general structural formula:
Figure PCTCN2019076409-appb-000001
Figure PCTCN2019076409-appb-000001
其中，所述结构通式中D1为第一基团，D2为所述第二基团，所述第一基团和所述第二基团为非对称基团。In the structural formula, D1 is a first group, D2 is the second group, and the first group and the second group are asymmetric groups.
进一步地，第一基团和第二基团的原料均各选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种。Further, the raw materials of the first group and the second group are each selected from 9,9′-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3, One of 6-dimethylcarbazole, phenothiazine, or acridinone.
为了能够得到所述的热活化延迟荧光单分子白光材料，本发明还提供了一种热活化延迟荧光单分子白光材料合成方法，包括如下步骤：第一混合溶液配制步骤，将第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井以及催化剂置于反应容器中进行充分反应，获得第一混合溶液，该第一混合溶液中包括第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井反应生成的中间体；第一萃取步骤，将所述第一混合溶液冷却至室温，萃取所述混合溶液并得到所述中间体；第二混合溶液配制步骤，将第二基团的原料以及所述中间体以及催化剂置于反应容器中，获得第二混合混合溶液，该第二混合溶液中包括所述中间体与所述第二基团的原料；第二萃取步骤，将所述第二混合溶液冷却至室温，萃取所述混合溶液并得到目标化合物，并分离纯化所述目标化合物，获得热活化延迟荧光单分子白光材料。In order to obtain the thermally activated delayed fluorescent single-molecule white light material, the present invention also provides a thermally activated delayed fluorescent single-molecule white light material synthesis method, which includes the following steps: a first mixed solution preparation step, the first group of The raw materials and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-both wells and catalyst are placed in the reaction vessel to fully react to obtain the first mixture Solution, the first mixed solution includes the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four well reaction The resulting intermediate; the first extraction step, cooling the first mixed solution to room temperature, extracting the mixed solution and obtaining the intermediate; the second mixed solution preparation step, the raw material of the second group and the The intermediate and the catalyst are placed in the reaction vessel to obtain a second mixed mixed solution, which includes the raw materials of the intermediate and the second group; a second extraction step, the second mixed solution Cool to room temperature, extract the mixed solution and obtain the target compound, and isolate and purify the The title compound was obtained monomolecular heat activated delayed fluorescent white light emitting material.
进一步地，所述第一基团和第二基团的原料均各选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种。其中，第一基团的原料与3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井的摩尔比1:1～1:5，所述第二基团的原料与所述中间体的摩尔比为1:1～1:5。Further, the raw materials of the first group and the second group are each selected from 9,9′-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, One of 3,6-dimethylcarbazole, phenothiazine, or acridinone. Among them, the molar ratio of the raw material of the first group to 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-metsutsui is 1: 1 ～ 1 : 5, the molar ratio of the raw material of the second group to the intermediate is 1: 1 to 1: 5.
进一步地，在所述第一混合溶液配制步骤中，反应时长为24小时，反应温度为100℃；在所述第二混合溶液配制步骤中，反应时长为24小时，反应温度为100℃。Further, in the first mixed solution preparation step, the reaction time is 24 hours and the reaction temperature is 100 ° C; in the second mixed solution preparation step, the reaction time is 24 hours and the reaction temperature is 100 ° C.
进一步地，在所述第一混合溶液配制步骤中以及在所述第二混合溶液配制步骤中，所述催化剂为醋酸钯、三叔丁基膦四氟硼酸盐、叔丁醇钠和甲苯。Further, in the first mixed solution preparation step and in the second mixed solution preparation step, the catalyst is palladium acetate, tri-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide and toluene.
进一步地，在所述第一混合溶液配制步骤中，将所述第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井、所述醋酸钯和所述三叔丁基膦四氟硼酸盐一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠以及除水除氧的甲苯，得到第一反应液。Further, in the step of preparing the first mixed solution, the raw materials of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2, 4,5-Four Sijing, the palladium acetate and the tri-tert-butylphosphine tetrafluoroborate are placed together in the reaction vessel, and then the reaction vessel is placed in an argon atmosphere The sodium tert-butoxide and toluene for removing water and oxygen are added to the reaction vessel to obtain a first reaction solution.
进一步地，在所述第二混合溶液配制步骤中，先将所述中间体、第二基团的原料、醋酸钯和三叔丁基膦四氟硼酸盐一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往反应容器中加入所述叔丁醇钠以及 除水除氧的甲苯，得到第二反应液。Further, in the step of preparing the second mixed solution, the intermediate, the raw material of the second group, palladium acetate and tri-tert-butylphosphine tetrafluoroborate are placed together in the reaction vessel, Then, the reaction container is placed in an argon atmosphere, and the sodium tert-butoxide and toluene in which water and oxygen are removed are added to the reaction container to obtain a second reaction liquid.
进一步地，所述第一萃取步骤包括将第一混合溶液倒入冰水中,并使用二氯甲烷萃取三次，合并有机相，得到所述热活化延迟荧光单分子白光材料；第二萃取步骤还包括将第二混合溶液倒入冰水中,并使用二氯甲烷萃取三次，合并有机相，得到所述热活化延迟荧光单分子白光材料。Further, the first extraction step includes pouring the first mixed solution into ice water, and extracting three times with dichloromethane, and combining the organic phases to obtain the thermally activated delayed fluorescent single molecule white light material; the second extraction step also includes The second mixed solution was poured into ice water, and extracted three times with dichloromethane, and the organic phases were combined to obtain the thermally activated delayed fluorescent single molecule white light material.
本发明还提供一种有机电致发光器件，包括一发光层，所述发光层的发光染料为所述热活化延迟荧光单分子白光材料。The invention also provides an organic electroluminescent device, which includes a light-emitting layer, and the luminescent dye of the light-emitting layer is the thermally activated delayed fluorescent monomolecular white light material.
有益效果Beneficial effect
本发明的热活化延迟荧光单分子白光材料，设计合成具有不同基团的D1-A-D2结构的分子体系，对D1和D2进行排列组合，使得D1-A-D2结构形成非对称结构，其具有较高的白光发光性能。The thermally activated delayed fluorescent single-molecule white light material of the present invention is designed to synthesize a molecular system of D1-A-D2 structure with different groups, and arrange and combine D1 and D2 so that the D1-A-D2 structure forms an asymmetric structure. Has a high white light emitting performance.
本发明的热活化延迟荧光单分子白光材料的合成方法，在最终合成物中，所合成的热活化延迟荧光单分子白光材料占比较高，有效的提高了热活化延迟荧光单分子白光材料合成率，使得采用本方法合成的热活化延迟荧光单分子白光材料具有较高的白光发光性能。In the method for synthesizing the thermally activated delayed fluorescent single molecule white light material of the present invention, in the final composition, the synthesized thermally activated delayed fluorescent single molecule white light material accounts for a relatively high proportion, effectively improving the synthesis rate of the thermally activated delayed fluorescent single molecule white light material , So that the thermally activated delayed fluorescent single molecule white light material synthesized by this method has higher white light emitting performance.
本发明的有机电致发光器件，采用本发明制备的热活化延迟荧光单分子白光材料，其发光效率高，而且使用寿命长。The organic electroluminescent device of the invention adopts the thermally activated delayed fluorescent single molecule white light material prepared by the invention, which has high luminous efficiency and long service life.
附图说明BRIEF DESCRIPTION
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly explain the technical solutions in the embodiments of the present invention, the drawings required in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those skilled in the art, without paying any creative work, other drawings can also be obtained based on these drawings.
图1为实施例1中的目标化合物光致发光光谱图。FIG. 1 is a photoluminescence spectrum chart of the target compound in Example 1. FIG.
图2为实施例1中的目标化合物的瞬态光谱图。FIG. 2 is a transient spectrum chart of the target compound in Example 1. FIG.
图3为应用例1的有机发光致电器的结构剖面图。3 is a cross-sectional view of the structure of an organic light emitting telephone of Application Example 1. FIG.
本发明的最佳实施方式Best Mode of the Invention
下面详细描述本发明的实施方式，所述实施方式的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施方式是示例性的，仅用于解释本发明，而不能理解为对本发明的限制。The embodiments of the present invention are described in detail below, and examples of the embodiments are shown in the drawings, in which the same or similar reference numerals indicate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the drawings are exemplary, and are only used to explain the present invention, and cannot be construed as limiting the present invention.
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二” 仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个所述特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In the description of the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", " Back, "Left", "Right", "Vertical", "Horizontal", "Top", "Bottom", "Inner", "Outer", "Clockwise", "Counterclockwise" etc. The positional relationship is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, Therefore, it cannot be understood as a limitation to the present invention. In addition, the terms “first” and “second” are used for description purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise specifically limited.
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接或可以相互通讯；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。In the description of the present invention, it should be noted that, unless otherwise clearly specified and defined, the terms "installation", "connection", and "connection" should be understood in a broad sense, for example, it can be fixed connection or detachable Connected, or integrally connected; it can be mechanical, electrical, or can communicate with each other; it can be directly connected, or it can be indirectly connected through an intermediary, it can be the connection between two elements or the interaction of two elements relationship. Those of ordinary skill in the art can understand the specific meanings of the above terms in the present invention according to specific situations.
在本发明中，除非另有明确的规定和限定，第一特征在第二特征之“上”或之“下”可以包括第一和第二特征直接接触，也可以包括第一和第二特征不是直接接触而是通过它们之间的另外的特征接触。而且，第一特征在第二特征“之上”、“上方”和“上面”包括第一特征在第二特征正上方和斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”包括第一特征在第二特征正下方和斜下方，或仅仅表示第一特征水平高度小于第二特征。In the present invention, unless otherwise clearly specified and defined, the first feature "above" or "below" the second feature may include the first and second features in direct contact, or may include the first and second features Contact not directly but through other features between them. Moreover, the first feature is “above”, “above” and “above” the second feature includes that the first feature is directly above and obliquely above the second feature, or simply means that the first feature is higher in level than the second feature. The first feature is "below", "below" and "below" the second feature includes that the first feature is directly below and obliquely below the second feature, or simply means that the first feature is less horizontal than the second feature.
下文的公开提供了许多不同的实施方式或例子用来实现本发明的不同结构。为了简化本发明的公开，下文中对特定例子的部件和设置进行描述。当然，它们仅仅为示例，并且目的不在于限制本发明。此外，本发明可以在不同例子中重复参考数字和/或参考字母，这种重复是为了简化和清楚的目的，其本身不指示所讨论各种实施方式和/或设置之间的关系。此外，本发明提供了的各种特定的工艺和材料的例子，但是本领域普通技术人员可以意识到其他工艺的应用和/或其他材料的使用。The following disclosure provides many different embodiments or examples for implementing different structures of the present invention. In order to simplify the disclosure of the present invention, the components and settings of specific examples are described below. Of course, they are only examples, and the purpose is not to limit the invention. In addition, the present invention may repeat reference numerals and / or reference letters in different examples. Such repetition is for the purpose of simplicity and clarity, and does not itself indicate the relationship between the various embodiments and / or settings discussed. In addition, the present invention provides examples of various specific processes and materials, but those of ordinary skill in the art may be aware of the application of other processes and / or the use of other materials.
本发明提出一类热活化延迟荧光单分子白光材料，本发明对目前研究火热的TADF材料进行深入研究，设计合成具有不同给体的D1-A-D2结构的分子体系。由第一基团的原料和第二基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井合成的热活化延迟荧光单分子白光材料，其结构通式为：The present invention proposes a class of thermally activated delayed fluorescent single-molecule white light materials. The present invention conducts in-depth research on the currently hot TADF materials, and designs and synthesizes molecular systems with different donors D1-A-D2 structures. Synthesized from the raw material of the first group and the raw material of the second group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-metsutsui Thermally activated delayed fluorescent single molecule white light material, its structural formula is:
Figure PCTCN2019076409-appb-000002
Figure PCTCN2019076409-appb-000002
其中，所述结构通式中D1为第一基团，D2为所述第二基团，所述第一基团和所述第二基团为非对称基团。In the structural formula, D1 is a first group, D2 is the second group, and the first group and the second group are asymmetric groups.
优选地，第一基团和第二基团的原料均各选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种。Preferably, the raw materials of the first group and the second group are each selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3, One of 6-dimethylcarbazole, phenothiazine, or acridinone.
具体的，第一基团和所述第二基团分子结构为如下任意一种，并且第一基团与第二基团不相同。Specifically, the molecular structure of the first group and the second group is any one of the following, and the first group and the second group are different.
Figure PCTCN2019076409-appb-000003
Figure PCTCN2019076409-appb-000003
根据所述第一基团和所述第二基团的选取原料不同，因此，最终生成的荧光单分子白光材料的结构通式可对应为式(1)-式(9)的一种：According to the selection of raw materials for the first group and the second group, the structural formula of the fluorescent single-molecule white light material finally generated may correspond to one of formula (1) -formula (9):
Figure PCTCN2019076409-appb-000004
Figure PCTCN2019076409-appb-000004
Figure PCTCN2019076409-appb-000005
Figure PCTCN2019076409-appb-000005
为了更加清楚的说明本发明中的热活化延迟荧光单分子白光材料，下面通过方法实施例1-3来具体说明。In order to more clearly describe the thermally activated delayed fluorescent monomolecular white light material in the present invention, the following will be specifically described by method examples 1-3.
方法实施例1Method Example 1
合成如式(1)所述的热活化延迟荧光单分子白光材料，其具体步骤如下所示。The specific steps for synthesizing the thermally activated delayed fluorescent monomolecular white light material as described in formula (1) are as follows.
第一混合溶液配制步骤：将第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井以及催化剂置于反应容器中进行充分反应，获得第一混合溶液，该第一混合溶液中包括第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井反应生成的中间体。第一基团的原 料均选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种，优选地为3,6-二甲基咔唑，第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井摩尔比为1:1，在其它实施例中也可为1:3,1:4,1:5。第一混合溶液配制步骤中，放入反应物顺序如下，将第一基团的原料(1.95g，10mmol)以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井(4.5g，10mmol)、醋酸钯(90mg，0.4mmol)和所述三叔丁基膦四氟硼酸盐(0.34g，1.2mmol)一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠NaOt-Bu(1.16g，12mmol)以及60ml除水除氧的甲苯，在110℃反应24小时得到反应液。The first mixed solution preparation step: the raw material of the first group and the 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells and catalyst Placed in a reaction vessel to perform a sufficient reaction to obtain a first mixed solution including the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -Intermediate produced by the reaction of 1, 2, 4, 4 and 5 wells. The raw materials of the first group are all selected from 9,9'-diphenylsilaccridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phen One of thiazine or acridinone, preferably 3,6-dimethylcarbazole, the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl The molar ratio of the base-1,2,4,5-averaged four wells is 1: 1, and in other embodiments may be 1: 3, 1: 4, 1: 5. In the preparation step of the first mixed solution, the order of putting the reactants is as follows, the raw material of the first group (1.95g, 10mmol) and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -1,2,4,5-All four wells (4.5g, 10mmol), palladium acetate (90mg, 0.4mmol) and the tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were placed together In the reaction vessel, place the reaction vessel in an argon atmosphere, and add the sodium tert-butoxide NaOt-Bu (1.16g, 12mmol) and 60ml of dehydrated and deoxygenated toluene to the reaction vessel And react at 110 ° C for 24 hours to obtain a reaction solution.
第一萃取步骤：将所述第一混合溶液冷却至室温，萃取所述混合溶液并得到所述中间体。在所述第一萃取步骤中，将第一混合溶液倒入200mL冰水中，二氯甲烷萃取三次，采用硅胶柱层析方法进行初次纯化所述目标化合物，得到初始纯化物，在所述硅胶柱层析方法过程中，所述二氯甲烷与所述正己烷的体积比为1:5，最终分离纯化得淡蓝色粉末3.37g，产率60％。下面通过检测设备按照检测要求对所制得的淡蓝色粉末进行分析，分析结果为：核磁氢谱、碳谱的结果为：1H NMR(300MHz,CD2Cl2,δ):8.43(s,2H),7.85(s,2H),7.83(d,J＝6.0Hz,2H),7.41(s,2H), 7.38(d,J＝6.3Hz,2H),2.57(s,12H),2.46(s,6H)。质谱结果为：MS(EI)m/z:[M]+calcd(理论值)for C32H28BrN5,561.15；found(实际值),561.10。元素分析结果为：Anal.(理论值)Calcd for C32H28BrN5:C 68.33,H 5.02,N 12.45；found(实际值):C 68.22,H 4.98,N 12.32.First extraction step: cooling the first mixed solution to room temperature, extracting the mixed solution and obtaining the intermediate. In the first extraction step, the first mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was firstly purified using a silica gel column chromatography method to obtain the initial purified product. During the chromatography method, the volume ratio of the dichloromethane to the n-hexane is 1: 5, and the final separation and purification gives 3.37 g of light blue powder with a yield of 60%. The light blue powder produced is analyzed by the detection equipment according to the detection requirements. The analysis results are: the results of nuclear magnetic hydrogen spectrum and carbon spectrum are: 1H NMR (300MHz, CD2Cl2, δ): 8.43 (s, 2H), 7.85 (s, 2H), 7.83 (d, J = 6.0 Hz, 2H), 7.41 (s, 2H), 7.38 (d, J = 6.3 Hz, 2H), 2.57 (s, 12H), 2.46 (s, 6H ). Mass spectrometry results are: MS (EI) m / z: [M] + calcd (theoretical value) for C32H28BrN5,561.15; found (actual value), 561.10. Elemental analysis results are: Anal. (Theoretical value) Calcd for C32H28BrN5: C 68.33, H 5.02, N 12.45; found (actual value): C 68.22, H 4.98, N 12.32.
第二混合溶液配制步骤：将第二基团的原料以及所述中间体以及催化剂置于反应容器中，获得第二混合溶液，该第二混合溶液中包括所述中间体与所述第二基团的原料。所述第二基团的原料均选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种，优选地为吩噻嗪，第二基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井摩尔比为1:1，在其它实施例中也可为1:3,1:4,1:5。在第二混合溶液配制步骤中，放入反应物顺序如下，中间体(1.0g，5mmol)以及第二基团(2.8g，5mmol)、醋酸钯(45mg，0.2mmol)和所述三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠NaOt-Bu(0.58g，6mmol)以及60ml除水除氧的甲苯，在110℃反应24小时得到反应液。The second mixed solution preparation step: placing the raw material of the second group, the intermediate and the catalyst in a reaction vessel to obtain a second mixed solution, the second mixed solution including the intermediate and the second group The raw material of the group. The raw materials of the second group are all selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole , One of phenothiazine or acridinone, preferably phenothiazine, the raw material of the second group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1, The molar ratio of 2,4,5-averaged four wells is 1: 1, in other embodiments it can be 1: 3, 1: 4, 1: 5. In the second mixed solution preparation step, the order of putting the reactants is as follows, the intermediate (1.0 g, 5 mmol) and the second group (2.8 g, 5 mmol), palladium acetate (45 mg, 0.2 mmol) and the tri-tert-butyl Phosphine tetrafluoroborate (0.17g, 0.6mmol) was placed in the reaction vessel together, the reaction vessel was placed in an argon atmosphere, and the sodium tert-butoxide was added to the reaction vessel NaOt-Bu (0.58 g, 6 mmol) and 60 ml of toluene dehydrated and deoxygenated were reacted at 110 ° C. for 24 hours to obtain a reaction solution.
第二萃取步骤：将所述第二混合溶液冷却至室温，萃取所述混合溶液并得到目标化合物，并分离纯化所述目标 化合物，获得热活化延迟荧光单分子白光材料。在所述第二萃取步骤中，将第二混合溶液倒入200mL冰水中，二氯甲烷萃取三次，采用硅胶柱层析方法进行初次纯化所述目标化合物，得到目标化合物，在所述硅胶柱层析方法过程中，所述二氯甲烷与所述正己烷的体积比为1:5，最终分离纯化得白色粉末1.7g，产率50％。下面通过检测设备按照检测要求对所制得的白色粉末进行分析，分析结果为：核磁氢谱、碳谱的结果为：11H NMR(300MHz,CD2Cl2,δ):8.45(s,2H),7.86(s,2H),7.83(d,J＝6.0Hz,2H),7.41(s,2H),7.38(d,J＝6.3Hz,2H),7.21(d,J＝6.3Hz,2H),7.16-6.93(m,6H),2.57(s,12H),2.46(s,6H)。质谱结果为：MS(EI)m/z:[M]+calcd(理论值)for C44H36N6S,680.27；found(实际值),680.10。元素分析结果为：Anal.(理论值)Calcd for C44H36N6S:C 77.62,H 5.33,N 12.34；found(实际值):C77.83,H 5.34,N 12.39。Second extraction step: cooling the second mixed solution to room temperature, extracting the mixed solution and obtaining the target compound, and separating and purifying the target compound to obtain a thermally activated delayed fluorescence single molecule white light material. In the second extraction step, the second mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was initially purified using a silica gel column chromatography method to obtain the target compound. During the analysis process, the volume ratio of the dichloromethane to the n-hexane was 1: 5, and the final separation and purification gave a white powder of 1.7 g with a yield of 50%. The following analysis is performed on the prepared white powder according to the detection requirements by the detection equipment. The analysis results are: the results of nuclear magnetic hydrogen spectrum and carbon spectrum are: 11H NMR (300MHz, CD2Cl2, δ): 8.45 (s, 2H), 7.86 ( s, 2H), 7.83 (d, J = 6.0 Hz, 2H), 7.41 (s, 2H), 7.38 (d, J = 6.3 Hz, 2H), 7.21 (d, J = 6.3 Hz, 2H), 7.16 6.93 (m, 6H), 2.57 (s, 12H), 2.46 (s, 6H). Mass spectrometry results are: MS (EI) m / z: [M] + calcd (theoretical value) for C44H36N6S, 680.27; found (actual value), 680.10. The elemental analysis result is: Anal. (Theoretical value) Calcd for C44H36N6S: C 77.62, H 5.33, N 12.34; found (actual value): C77.83, H 5.34, N 12.39.
制备得到的目标化合物1的优秀性能如图1和2所示。The excellent performance of the prepared target compound 1 is shown in Figures 1 and 2.
本方法实施例1的化学反应过程如下：The chemical reaction process of Example 1 of the method is as follows:
Figure PCTCN2019076409-appb-000006
Figure PCTCN2019076409-appb-000006
方法实施例2Method Example 2
合成如式(4)所述的热活化延迟荧光单分子白光材料，其具体步骤如下所示。The specific steps for synthesizing the thermally activated delayed fluorescent monomolecular white light material as described in formula (4) are as follows.
第一混合溶液配制步骤，将第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井以及催化剂置于反应容器中进行充分反应，获得第一混合溶液，该第一混合溶液中包括第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井反应生成的中间体。第一基团的原料均选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种，优选地为9,9’-二苯基硅代吖啶，第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井摩尔比为1:1，在其它实施例中也可为1:3,1:4,1:5。在第一混合溶液配制步骤放入反应物顺序如下，将第一基团的原料(3.5g，10mmol)以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井 (4.5g，10mmol)、醋酸钯(90mg，0.4mmol)和所述三叔丁基膦四氟硼酸盐(0.34g，1.2mmol)一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠NaOt-Bu(1.16g，12mmol)以及60ml除水除氧的甲苯，在110℃反应24小时得到反应液。The first mixed solution preparation step is to combine the raw materials of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells and catalyst Placed in a reaction vessel to perform a sufficient reaction to obtain a first mixed solution including the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -Intermediate produced by the reaction of 1, 2, 4, 4 and 5 wells. The raw materials of the first group are all selected from 9,9'-diphenylsilaccridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phen One of thiazine or acridinone, preferably 9,9'-diphenylsilicoacridine, the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5' -The molar ratio of tetramethyl-1,2,4,5-meat tetrahedron is 1: 1, and in other embodiments may be 1: 3, 1: 4, 1: 5. The order of putting the reactants in the preparation step of the first mixed solution is as follows. The raw materials of the first group (3.5g, 10mmol) and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl- 1,2,4,5-All four wells (4.5g, 10mmol), palladium acetate (90mg, 0.4mmol) and the tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2mmol) were placed together in the In the reaction vessel, place the reaction vessel in an argon atmosphere, and add the sodium tert-butoxide NaOt-Bu (1.16 g, 12 mmol) and 60 ml of dehydrated and deoxygenated toluene to the reaction vessel. The reaction liquid was obtained by reacting at 110 ° C for 24 hours.
第一萃取步骤，将所述第一混合溶液冷却至室温，萃取所述混合溶液并得到中间体；在所述第一萃取步骤中，将第一混合溶液倒入200mL冰水中，二氯甲烷萃取三次，采用硅胶柱层析方法进行初次纯化所述目标化合物，得到目标化合物，在所述硅胶柱层析方法过程中，所述二氯甲烷与所述正己烷的体积比为1:5，最终分离纯化得淡蓝色粉末3.6g，产率50％。下面通过检测设备按照检测要求对所制得的白色粉末进行分析，分析结果为：核磁氢谱、碳谱的结果为：1H NMR(300MHz,CD2Cl2,δ):7.42-7.38(m,14H),7.34(s,2H),7.30-7.28(m,4H),7.03(t,J＝6.9Hz,2H),2.57(s,12H),2.57(s,12H)。质谱结果为：MS(EI)m/z:[M]+calcd(理论值)for C42H34BrN5Si,445.97；found(实际值),446.00。In the first extraction step, the first mixed solution was cooled to room temperature, the mixed solution was extracted and an intermediate was obtained; in the first extraction step, the first mixed solution was poured into 200 mL of ice water and extracted with dichloromethane Three times, the silica gel column chromatography method was used for the first time to purify the target compound to obtain the target compound. During the silica gel column chromatography method, the volume ratio of the dichloromethane to the n-hexane was 1: 5. Isolation and purification gave 3.6 g of light blue powder with a yield of 50%. The following analysis is performed on the prepared white powder according to the detection requirements by the detection equipment. The analysis results are: the results of nuclear magnetic hydrogen spectrum and carbon spectrum are: 1H NMR (300MHz, CD2Cl2, δ): 7.42-7.38 (m, 14H), 7.34 (s, 2H), 7.30-7.28 (m, 4H), 7.03 (t, J = 6.9 Hz, 2H), 2.57 (s, 12H), 2.57 (s, 12H). The mass spectrometry result is: MS (EI) m / z: [M] + calcd (theoretical value) for C42H34BrN5Si, 445.97; found (actual value), 446.00.
元素分析结果为：Calcd(理论值)for C42H34BrN5Si:C 70.38,H 4.78,N 9.77；found(实际值):C 70.22,H 4.68,N 9.56。The elemental analysis results are: Calcd (theoretical value) for C42H34BrN5Si: C 70.38, H 4.78, N 9.77; found (actual value): C 70.22, H 4.68, N 9.56.
第二混合溶液配制步骤，将第二基团的原料以及所述中间体以及催化剂置于反应容器中，获得第二混合溶液，该第二混合溶液中包括所述中间体与所述第二基团的原料；第二基团的原料均选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种，优选地为亚氨基芪，第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井摩尔比为1:1，在其它实施例中也可为1:3,1:4,1:5。在所述第二混合溶液配制步骤中，放入反应物顺序如下，中间体2(2.86g，4mmol)，第二基团的原料(0.77g，4mmol)，醋酸钯(38mg，0.17mmol)和三叔丁基膦四氟硼酸盐(0.14g，0.5mmol)，一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠NaOt-Bu(0.48g，5mmol)以及60ml除水除氧的甲苯，在110℃反应24小时得到反应液。In the second mixed solution preparation step, the raw material of the second group, the intermediate, and the catalyst are placed in a reaction vessel to obtain a second mixed solution, and the second mixed solution includes the intermediate and the second group The raw materials of the group; the raw materials of the second group are selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethyl One of carbazole, phenothiazine, or acridinone, preferably iminostilbene, the raw material of the first group, and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl- The molar ratio of 1,2,4,5-averaged four wells is 1: 1, in other embodiments it can be 1: 3, 1: 4, 1: 5. In the preparation step of the second mixed solution, the order of putting the reactants is as follows, intermediate 2 (2.86 g, 4 mmol), raw material of the second group (0.77 g, 4 mmol), palladium acetate (38 mg, 0.17 mmol) and Tri-tert-butylphosphine tetrafluoroborate (0.14g, 0.5mmol), placed together in the reaction vessel, then placed the reaction vessel in an argon atmosphere, and added the reaction vessel to the reaction vessel Sodium tert-butoxide NaOt-Bu (0.48 g, 5 mmol) and 60 ml of toluene dehydrated and deoxygenated were reacted at 110 ° C. for 24 hours to obtain a reaction solution.
第二萃取步骤，将所述第二混合溶液冷却至室温，萃取所述混合溶液并得到目标化合物，并分离纯化所述目标化合物，获得热活化延迟荧光单分子白光材料。在所述第二萃取步骤中，将第二混合溶液倒入200mL冰水中，二氯甲烷萃取三次，采用硅胶柱层析方法进行初次纯化所述目标化合物，得到目标化合物，在所述硅胶柱层析方法过程中，所述二氯甲烷与所述正己烷的体积比为1:5，最终 分离纯化得白色粉末1.2g，产率36％。下面通过检测设备按照检测要求对所制得的白色粉末进行分析，分析结果为：核磁氢谱、碳谱的结果为：1H NMR(300MHz,CD2Cl2,δ):7.52-7.46(m,12H),7.34(s,2H),7.31(s,2H),7.29-7.23(m,4H),7.19-7.03(m,10H),6.99(s,2H),2.57(s,12H)。质谱结果为：MS(EI)m/z:[M]+calcd(理论值)for C56H44N6Si,828.34；found(实际值),828.30。元素分析结果为：Calcd(理论值)for C56H44N6Si:C 81.23,H 5.35,N 10.14；found(实际值):C 81.21,H 5.34,N 10.09。In the second extraction step, the second mixed solution is cooled to room temperature, the mixed solution is extracted and a target compound is obtained, and the target compound is separated and purified to obtain a thermally activated delayed fluorescence single molecule white light material. In the second extraction step, the second mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was initially purified using a silica gel column chromatography method to obtain the target compound. During the analysis process, the volume ratio of the dichloromethane to the n-hexane was 1: 5, and finally the white powder was separated and purified to obtain 1.2 g, with a yield of 36%. The following analysis is performed on the prepared white powder according to the detection requirements by the detection equipment. The analysis results are: the results of nuclear magnetic hydrogen spectrum and carbon spectrum are: 1H NMR (300MHz, CD2Cl2, δ): 7.52-7.46 (m, 12H), 7.34 (s, 2H), 7.31 (s, 2H), 7.29-7.23 (m, 4H), 7.19-7.03 (m, 10H), 6.99 (s, 2H), 2.57 (s, 12H). Mass spectrometry results are: MS (EI) m / z: [M] + calcd (theoretical value) for C56H44N6Si, 828.34; found (actual value), 828.30. The elemental analysis results are: Calcd (theoretical value) for C56H44N6Si: C 81.23, H 5.35, N 10.14; found (actual value): C 81.21, H 5.34, N 10.09.
化学反应方程式如下：The chemical reaction equation is as follows:
Figure PCTCN2019076409-appb-000007
Figure PCTCN2019076409-appb-000007
方法实施例3Method Example 3
合成如式(8)所述的热活化延迟荧光单分子白光材料，其具体步骤如下所示。The specific steps for synthesizing the thermally activated delayed fluorescent monomolecular white light material as described in formula (8) are as follows.
第一混合溶液配制步骤，将第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井以及催化剂置于 反应容器中进行充分反应，获得第一混合溶液，该第一混合溶液中包括第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井反应生成的中间体。第一基团的原料均选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种，优选地为3,6-二甲基-螺硅烷吖啶，第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井摩尔比为1:1，在其它实施例中也可为1:3,1:4,1:5。在第一混合溶液配制步骤中，放入反应物顺序如下，将3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井(4.5g，10mmol)，3,6-二甲基-螺硅烷吖啶(3.75g，10mmol)，醋酸钯(90mg，0.4mmol)和三叔丁基膦四氟硼酸盐(0.34g，1.2mmol)，一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠NaOt-Bu(1.16g，12mmol)以及60ml除水除氧的甲苯，在110℃反应24小时得到第一混合溶液。The first mixed solution preparation step is to combine the raw materials of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells and catalyst Placed in a reaction vessel to perform a sufficient reaction to obtain a first mixed solution including the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -Intermediate produced by the reaction of 1, 2, 4, 4 and 5 wells. The raw materials of the first group are all selected from 9,9'-diphenylsilaccridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phen One of thiazine or acridinone, preferably 3,6-dimethyl-spirosilane acridine, the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5' -The molar ratio of tetramethyl-1,2,4,5-meat tetrahedron is 1: 1, and in other embodiments may be 1: 3, 1: 4, 1: 5. In the first mixed solution preparation step, the order of putting the reactants is as follows, 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells (4.5g, 10mmol), 3,6-dimethyl-spirosilane acridine (3.75g, 10mmol), palladium acetate (90mg, 0.4mmol) and tri-tert-butylphosphine tetrafluoroborate (0.34g, 1.2 mmol), placed together in the reaction vessel, then placed the reaction vessel in an argon atmosphere, and added the sodium tert-butoxide NaOt-Bu (1.16 g, 12 mmol) and 60 ml to the reaction vessel Toluene which was dehydrated and deoxygenated was reacted at 110 ° C for 24 hours to obtain a first mixed solution.
第一萃取步骤，将所述第一混合溶液冷却至室温，萃取第一混合溶液并得到中间体；在所述第一萃取步骤，将第一混合溶液倒入200mL冰水中，二氯甲烷萃取三次，采用硅胶柱层析方法进行初次纯化所述目标化合物，得到目标化合物，在所述硅胶柱层析方法过程中，所述二氯甲烷与所述正己烷的体积比为1:5，最终分离纯化得淡蓝色 粉末4.0g，产率54％。通过检测设备按照检测要求对所制得的白色粉末进行分析，分析结果为：核磁氢谱、碳谱的结果为：1H NMR(300MHz,CD2Cl2,δ):8.43(s,2H),7.88(s,2H),7.60(d,J＝6.3Hz,2H),7.46-7.21(m,8H),7.09-6.98(m,6H),2.57(s,12H)。质谱结果为：MS(EI)m/z:MS(EI)m/z:[M]+calcd(理论值)for C44H36BrN5Si,741.19；found(实际值),741.10。元素分析结果为：Calcd(理论值)for C44H36BrN5Si:C 71.15,H 4.89,N 9.43；found(实际值)0:C 71.10,H 4.76,N 9.32.。In the first extraction step, the first mixed solution was cooled to room temperature, the first mixed solution was extracted and an intermediate was obtained; in the first extraction step, the first mixed solution was poured into 200 mL of ice water and extracted three times with dichloromethane , Using a silica gel column chromatography method for the first purification of the target compound to obtain the target compound, in the process of the silica gel column chromatography method, the volume ratio of the dichloromethane and the n-hexane is 1: 5, the final separation Purified to give light blue powder 4.0g, yield 54%. The obtained white powder was analyzed according to the detection requirements by the detection equipment, and the analysis results were: the results of nuclear magnetic hydrogen spectrum and carbon spectrum were: 1H NMR (300MHz, CD2Cl2, δ): 8.43 (s, 2H), 7.88 (s , 2H), 7.60 (d, J = 6.3 Hz, 2H), 7.46-7.21 (m, 8H), 7.09-6.98 (m, 6H), 2.57 (s, 12H). Mass spectrometry results are: MS (EI) m / z: MS (EI) m / z: [M] + calcd (theoretical value) for C44H36BrN5Si, 741.19; found (actual value), 741.10. The elemental analysis results are: Calcd (theoretical value) for C44H36BrN5Si: C 71.15, H 4.89, N 9.43; found (actual value) 0: C 71.10, H 4.76, N 9.32.
第二混合溶液配制步骤，将第二基团的原料以及所述中间体以及催化剂置于反应容器中，获得第二混合溶液，该第二混合溶液中包括所述中间体与所述第二基团的原料；第二基团的原料均选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种，优选地为吖啶酮，第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井摩尔比为1:1，在其它实施例中也可为1:3,1:4,1:5。在第二混合溶液配制步骤中，放入反应物顺序如下，中间体3(3.7g，5mmol)，吖啶酮(1.0g，5mmol)，醋酸钯(45mg，0.2mmol)和三叔丁基膦四氟硼酸盐(0.17g，0.6mmol)，然后在手套箱中加入NaOt-Bu(0.58g，6mmol)，一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述 反应容器中加入所述叔丁醇钠NaOt-Bu(0.58g，6mmol)以及60ml除水除氧的甲苯，在110℃反应24小时得到反应液。In the second mixed solution preparation step, the raw material of the second group, the intermediate, and the catalyst are placed in a reaction vessel to obtain a second mixed solution, and the second mixed solution includes the intermediate and the second group The raw materials of the group; the raw materials of the second group are selected from 9,9'-diphenylsilicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethyl One of carbazole, phenothiazine or acridinone, preferably acridinone, the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl- The molar ratio of 1,2,4,5-averaged four wells is 1: 1, in other embodiments it can be 1: 3, 1: 4, 1: 5. In the second mixed solution preparation step, the order of putting the reactants is as follows, intermediate 3 (3.7g, 5mmol), acridinone (1.0g, 5mmol), palladium acetate (45mg, 0.2mmol) and tri-tert-butylphosphine Tetrafluoroborate (0.17g, 0.6mmol), then add NaOt-Bu (0.58g, 6mmol) to the glove box, place them together in the reaction vessel, and then place the reaction vessel in an argon atmosphere To the reaction vessel, the sodium tert-butoxide NaOt-Bu (0.58g, 6mmol) and 60ml of dehydrated and deoxygenated toluene were added and reacted at 110 ° C for 24 hours to obtain a reaction solution.
第二萃取步骤，将所述第二混合溶液冷却至室温，萃取所述混合溶液并得到目标化合物，并分离纯化所述目标化合物，获得热活化延迟荧光单分子白光材料。在第二萃取步骤中，将第二混合溶液倒入200mL冰水中，二氯甲烷萃取三次，采用硅胶柱层析方法进行初次纯化所述目标化合物，得到目标化合物，在所述硅胶柱层析方法过程中，所述二氯甲烷与所述正己烷的体积比为1:5，最终分离纯化得白色粉末1.1g，产率26％。通过检测设备按照检测要求对所制得的白色粉末进行分析，分析结果为：核磁氢谱、碳谱的结果为：1H NMR(300MHz,CD2Cl2,δ):7.88(s,2H),7.66(d,J＝6.3Hz,2H),7.60(d,J＝6.9Hz,2H),7.50-7.23(m,16H),7.17(t,J＝6.3Hz,2H),7.03(t,J＝6.6Hz,2H),2.57(s,12H),2.46(s,6H)。In the second extraction step, the second mixed solution is cooled to room temperature, the mixed solution is extracted and a target compound is obtained, and the target compound is separated and purified to obtain a thermally activated delayed fluorescence single molecule white light material. In the second extraction step, the second mixed solution was poured into 200 mL of ice water, extracted three times with dichloromethane, and the target compound was firstly purified using a silica gel column chromatography method to obtain the target compound. In the silica gel column chromatography method During the process, the volume ratio of the dichloromethane to the n-hexane was 1: 5, and the final separation and purification gave 1.1 g of white powder with a yield of 26%. The obtained white powder is analyzed according to the detection requirements by the detection equipment. The analysis results are: the results of nuclear magnetic hydrogen spectrum and carbon spectrum are: 1H NMR (300MHz, CD2Cl2, δ): 7.88 (s, 2H), 7.66 (d , J = 6.3 Hz, 2H), 7.60 (d, J = 6.9 Hz, 2H), 7.50-7.23 (m, 16H), 7.17 (t, J = 6.3 Hz, 2H), 7.03 (t, J = 6.6 Hz , 2H), 2.57 (s, 12H), 2.46 (s, 6H).
质谱结果为：MS(EI)m/z:[M]+calcd(理论值)for C57H44N6OSi,856.33；found(实际值)0,856.23。元素分析结果为Calcd(理论值)for C57H44N6OSi:C 79.88,H 5.17,N 9.81；found(实际值):C79.83,H 5.14,N 9.69.。Mass spectrometry results are: MS (EI) m / z: [M] + calcd (theoretical value) for C57H44N6OSi, 856.33; found (actual value) 0,856.23. The elemental analysis result is Calcd (theoretical value) for C57H44N6OSi: C 79.88, H 5.17, N 9.81; found (actual value): C79.83, H 5.14, N 9.69.
化学反应方程式如下：The chemical reaction equation is as follows:
Figure PCTCN2019076409-appb-000008
Figure PCTCN2019076409-appb-000008
其他结构的热活化延迟荧光单分子白光材料，如式(2)、式(9)等所示，其制备方法参见方法实施例1-方法实施例3，其主要的制备步骤一致，唯一区别在于所选用的第一基团和第二基团的原料不同，因此不再一一赘述。Other structures of thermally activated delayed fluorescent monomolecular white light materials, as shown in formula (2), formula (9), etc., for the preparation method, see method example 1 to method example 3, the main preparation steps are the same, the only difference is The raw materials of the first group and the second group are different, so they will not be described one by one.
应用例Application examples
本发明所公开的热活化延迟荧光单分子白光材料可应用在有机电致发光器件中，具体的应用于发光层。单分子白光材料以其优秀的发光性能，没有相分离等优势被认为是最具潜力的白光照明材料。The thermally activated delayed fluorescent single-molecule white light material disclosed in the present invention can be applied to organic electroluminescent devices, and is specifically applied to a light-emitting layer. Monomolecular white light materials are considered to be the most promising white light illumination materials due to their excellent light-emitting performance and no phase separation.
本发明对目前研究火热的TADF材料进行深入研究，设计合成具有不同给体的D1-A-D2结构的分子体系，对D1和D2进行排列组合，选择具有优秀白光发光性能的分子。为了将这种白光分子应用于显示装置中，一般显示装置包括有机电致发光器件，发光层常设于有机电致发光器件中，本应用例中以一种有机电致发光器件对本发明的应 用作进一步说明。The present invention conducts in-depth research on the currently hot TADF materials, designs and synthesizes molecular systems of D1-A-D2 structures with different donors, arranges and combines D1 and D2, and selects molecules with excellent white light emitting properties. In order to apply such white light molecules to a display device, a general display device includes an organic electroluminescent device, and the light-emitting layer is permanently located in the organic electroluminescent device. In this application example, an organic electroluminescent device is used for the application of the present invention. Further explanation.
如图1和2所示，目标化合物1优秀的性能可以将其应用与所述有机致电发光器件10。As shown in FIGS. 1 and 2, the excellent performance of the target compound 1 can be applied to the organic light-emitting device 10.
如图3所示，有机电致发光器件10包括衬底层11、第一功能层12、发光层13、第二功能层14和阴极层15；所述衬底层11为导电玻璃；第一功能层12为空穴传输层，并且贴附于衬底11的一侧；发光层13贴附于第一功能层12远离衬底11的一侧；第二功能层14为电子传输层，并且贴附于发光层13远离第一功能层12的一侧；阴极层15贴附于第二功能层14远离发光层13的一侧。其中所述衬底1的材料可以是玻璃和/或导电玻璃(ITO)，其厚度一般为45-55nm，所述空穴传输和注入层材料可以是聚3,4-乙撑二氧噻吩、聚苯乙烯磺酸盐和PEDOT:PSS中的一种，其厚度一般为45-55nm；所述电子传输层的材料可以是1,3,5-三(3-(3-吡啶基)苯基)苯/TmPyPB，其厚度一般为35-45nm；所述阴极层的材料可以是氟化锂/铝，其厚度一般为95-105nm。所述发光层13采用本发明的热活化延迟荧光单分子白光材料(40nm)作为发光层的材料，并在高真空条件下一次蒸镀单分子白光材料。As shown in FIG. 3, the organic electroluminescent device 10 includes a substrate layer 11, a first functional layer 12, a light-emitting layer 13, a second functional layer 14, and a cathode layer 15; the substrate layer 11 is conductive glass; the first functional layer 12 is a hole transport layer and is attached to the side of the substrate 11; the light-emitting layer 13 is attached to the side of the first functional layer 12 away from the substrate 11; the second functional layer 14 is an electron transport layer and is attached The side of the light-emitting layer 13 away from the first functional layer 12; the cathode layer 15 is attached to the side of the second functional layer 14 away from the light-emitting layer 13. The material of the substrate 1 may be glass and / or conductive glass (ITO), the thickness of which is generally 45-55 nm, and the material of the hole transport and injection layer may be poly 3,4-ethylenedioxythiophene, Polystyrene sulfonate and PEDOT: PSS, the thickness of which is generally 45-55nm; the material of the electron transport layer may be 1,3,5-tris (3- (3-pyridyl) phenyl ) Benzene / TmPyPB, whose thickness is generally 35-45nm; the material of the cathode layer may be lithium fluoride / aluminum, and its thickness is generally 95-105nm. The light-emitting layer 13 uses the thermally activated delayed fluorescent monomolecular white light material (40 nm) of the present invention as the material of the light-emitting layer, and the monomolecular white light material is vapor-deposited at a time under high vacuum conditions.
下面为了充分说明本发明的有机电致发光器件的性能，对本发明的电致发光器件进行性能测量，其中所述有机电致发光器件的电流-亮度-电压特性是由带有校正过的 硅光电二极管的Keithley源测量系统(Keithley 2400 Sourcemeter、Keithley 2000 Currentmeter)完成的，电致发光光谱是由法国JY公司SPEX CCD3000光谱仪测量的，所有测量均在室温大气中完成。其中所述器件的性能数据如下表1所示：In order to fully illustrate the performance of the organic electroluminescent device of the present invention, the performance of the electroluminescent device of the present invention is measured, wherein the current-luminance-voltage characteristic of the organic electroluminescent device is The diode's Keithley source measurement system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) was completed, and the electroluminescence spectrum was measured by the French JY company SPEX CCD3000 spectrometer, all measurements were completed in the room temperature atmosphere. The performance data of the device is shown in Table 1 below:
表1为有机电致发光器件的最高亮度、启动电压等各项性能参数。Table 1 shows the performance parameters of the organic electroluminescent device such as the highest brightness and starting voltage.
器件Device 最高亮度(cd/m 2) Maximum brightness (cd / m 2 ) 启动电压(V)Starting voltage (V) CIECIE 最大外量子效率(％)Maximum external quantum efficiency (%)
器件1 Device 1 986986 7.37.3 (0.24,0.38)(0.24,0.38) 7.37.3
器件2 Device 2 700700 7.07.0 (0.32,0.33)(0.32,0.33) 6.06.0
由上表1可知，器件1为本发明的有机电致发光器件，器件2为对比器件，器件1与器件2光谱CIE坐标都为白光。可以看出本发明提供的器件1具有较高的最高亮度，相比对比器件2发光亮度提高，量子效率也有所提高，It can be seen from Table 1 above that Device 1 is an organic electroluminescent device of the present invention, Device 2 is a comparative device, and the spectral CIE coordinates of Device 1 and Device 2 are both white light. It can be seen that the device 1 provided by the present invention has a higher maximum brightness. Compared with the comparison device 2, the light emitting brightness is improved, and the quantum efficiency is also improved.
以上对本发明实施例提供的显影方法以及金属层的图形化处理方法进行了详细介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明。同时，对于本领域的技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。The development method and the patterning method of the metal layer provided by the embodiments of the present invention are described in detail above. Specific examples are used in this article to explain the principles and implementation of the present invention. The descriptions of the above embodiments are only for understanding this invention. At the same time, for those skilled in the art, according to the ideas of the present invention, there will be changes in the specific implementation and application scope. In summary, the content of this specification should not be construed as limiting the present invention.

Claims (10)

  1. 一种热活化延迟荧光单分子白光材料，其中，为由第一基团的原料和第二基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井合成的热活化延迟荧光单分子白光材料，其结构通式为：A thermally activated delayed fluorescent monomolecular white light material, which is composed of the raw material of the first group and the raw material of the second group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -The thermally activated delayed fluorescence monomolecular white light material synthesized by 1, 2, 4, 4 and 5-well four wells has the general structural formula:
    Figure PCTCN2019076409-appb-100001
    Figure PCTCN2019076409-appb-100001
    其中，所述结构通式中D1为第一基团，D2为所述第二基团，所述第一基团和所述第二基团为非对称基团。In the structural formula, D1 is a first group, D2 is the second group, and the first group and the second group are asymmetric groups.
  2. 根据权利要求1所述的热活化延迟荧光单分子白光材料，其中，所述结构通式中，所述第一基团和所述第二基团的原料均选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种。The thermally activated delayed fluorescence monomolecular white light material according to claim 1, wherein in the structural formula, the raw materials of the first group and the second group are selected from 9,9'-diphenyl One of silicoacridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phenothiazine, or acridinone.
  3. 一种热活化延迟荧光单分子白光材料合成方法，其包括如下步骤：A synthetic method of thermally activated delayed fluorescent single-molecule white light material includes the following steps:
    第一混合溶液配制步骤，将第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井以及催化剂置于反应容器中进行充分反应，获得第一混合溶液，该第一混合溶液中包括第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井反应生成的中间体；The first mixed solution preparation step is to combine the raw materials of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-all four wells and catalyst Placed in a reaction vessel to perform a sufficient reaction to obtain a first mixed solution including the raw material of the first group and 3,3'-dibromo-1,5,1 ', 5'-tetramethyl -Intermediate produced by the reaction of 1, 2, 4, 4 and 5 wells;
    第一萃取步骤，将所述第一混合溶液冷却至室温， 萃取所述混合溶液并得到所述中间体；In the first extraction step, the first mixed solution is cooled to room temperature, the mixed solution is extracted and the intermediate is obtained;
    第二混合溶液配制步骤，将第二基团的原料以及所述中间体以及催化剂置于反应容器中，获得第二混合溶液，该第二混合溶液中包括所述中间体与所述第二基团的原料；In the second mixed solution preparation step, the raw material of the second group, the intermediate, and the catalyst are placed in a reaction vessel to obtain a second mixed solution, and the second mixed solution includes the intermediate and the second group The raw materials of the group;
    第二萃取步骤，将所述第二混合溶液冷却至室温，萃取所述混合溶液并得到目标化合物，并分离纯化所述目标化合物，获得热活化延迟荧光单分子白光材料。In the second extraction step, the second mixed solution is cooled to room temperature, the mixed solution is extracted and a target compound is obtained, and the target compound is separated and purified to obtain a thermally activated delayed fluorescence single molecule white light material.
  4. 根据权利要求3所述的热活化延迟荧光单分子白光材料合成方法，其中，所述第一基团和所述第二基团的原料均各选自9,9’-二苯基硅代吖啶、亚氨基芪、3,6-二甲基-螺硅烷吖啶、3,6-二甲基咔唑、吩噻嗪或吖啶酮的一种；The method for synthesizing a thermally activated delayed fluorescent single-molecule white light material according to claim 3, wherein the raw materials of the first group and the second group are each selected from 9,9'-diphenyl silicon acridine One of pyridine, iminostilbene, 3,6-dimethyl-spirosilane acridine, 3,6-dimethylcarbazole, phenothiazine or acridinone;
    所述第一基团的原料与3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井的摩尔比1:1～1:5，所述第二基团的原料与所述中间体的摩尔比为1:1～1:5。The molar ratio of the raw material of the first group to 3,3'-dibromo-1,5,1 ', 5'-tetramethyl-1,2,4,5-metsutsui 1: 1 to 1 : 5, the molar ratio of the raw material of the second group to the intermediate is 1: 1 to 1: 5.
  5. 根据权利要求3所述的热活化延迟荧光单分子白光材料合成方法，其中，在所述第一混合溶液配制步骤中，反应时长为24小时，反应温度为100℃；The method for synthesizing a thermally activated delayed fluorescent single molecule white light material according to claim 3, wherein in the step of preparing the first mixed solution, the reaction time is 24 hours and the reaction temperature is 100 ° C;
    在所述第二混合溶液配制步骤中，反应时长为24小时，反应温度为100℃。In the step of preparing the second mixed solution, the reaction time is 24 hours and the reaction temperature is 100 ° C.
  6. 根据权利要求3所述的热活化延迟荧光单分子白 光材料合成方法，其中，在所述第一混合溶液配制步骤中以及在所述第二混合溶液配制步骤中，所述催化剂为醋酸钯、三叔丁基膦四氟硼酸盐、叔丁醇钠和甲苯。The method for synthesizing a thermally activated delayed fluorescent single molecule white light material according to claim 3, wherein in the first mixed solution preparation step and in the second mixed solution preparation step, the catalyst is palladium acetate, three Tert-butylphosphine tetrafluoroborate, sodium tert-butoxide and toluene.
  7. 根据权利要求6所述的热活化延迟荧光单分子白光材料合成方法，其中，在所述第一混合溶液配制步骤中，所述第一基团的原料以及3,3’-二溴-1,5,1’,5’-四甲基-1,2,4,5-均四井、所述醋酸钯和所述三叔丁基膦四氟硼酸盐一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠以及除水除氧的甲苯，得到第一反应液。The thermally activated delayed fluorescent single molecule white light material synthesis method according to claim 6, wherein in the first mixed solution preparation step, the raw material of the first group and 3,3'-dibromo-1, 5,1 ', 5'-tetramethyl-1,2,4,5-metsutsui, the palladium acetate and the tri-tert-butylphosphine tetrafluoroborate are placed together in the reaction vessel, Then, the reaction vessel is placed in an argon atmosphere, and the sodium tert-butoxide and toluene to remove water and oxygen are added to the reaction vessel to obtain a first reaction solution.
  8. 根据权利要求6所述的热活化延迟荧光单分子白光材料合成方法，其中，在所述第二混合溶液配制步骤中，所述中间体、所述第二基团的原料、所述醋酸钯和所述三叔丁基膦四氟硼酸盐一起放置于所述反应容器中，再将所述反应容器放置于氩气环境中，并往所述反应容器中加入所述叔丁醇钠以及除水除氧的甲苯，得到第二反应液。The method for synthesizing a thermally activated delayed fluorescence single molecule white light material according to claim 6, wherein in the step of preparing the second mixed solution, the intermediate, the raw material of the second group, the palladium acetate and The tri-tert-butylphosphine tetrafluoroborate is placed together in the reaction vessel, and then the reaction vessel is placed in an argon atmosphere, and the sodium tert-butoxide is added to the reaction vessel and removed Toluene deoxygenated with water to obtain a second reaction liquid.
  9. 根据权利要求4所述的热活化延迟荧光单分子白光材料合成方法，其中，The method for synthesizing a thermally activated delayed fluorescent monomolecular white light material according to claim 4, wherein
    所述第一萃取步骤中包括将第一混合溶液倒入冰水中,并使用二氯甲烷多次萃取，合并有机相，得到所述热活化延迟荧光单分子白光材料；In the first extraction step, the first mixed solution is poured into ice water, and extracted multiple times with dichloromethane, and the organic phases are combined to obtain the thermally activated delayed fluorescent single molecule white light material;
    所述第二萃取步骤还包括将第二混合溶液倒入冰水 中,并使用二氯甲烷多次萃取，合并有机相，得到所述热活化延迟荧光单分子白光材料。The second extraction step further includes pouring the second mixed solution into ice water, extracting with dichloromethane multiple times, and combining the organic phases to obtain the thermally activated delayed fluorescent single molecule white light material.
  10. 一种有机电致发光器件，包括一发光层，其中，所述发光层的发光染料为权利要求1所述的热活化延迟荧光单分子白光材料。An organic electroluminescent device includes a light-emitting layer, wherein the light-emitting dye of the light-emitting layer is the thermally activated delayed fluorescent single molecule white light material of claim 1.
PCT/CN2019/076409 2018-10-23 2019-02-28 Thermally activated delayed fluorescence monomolecular white light material and synthesizing method therefor, and organic electroluminescent device WO2020082656A1 (en)

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