Polysulfide aromatic hydrocarbon thermal activation delayed fluorescence compound and preparation method thereof
The thermally activated delayed fluorescent compound designed by polysulfur aromatic hydrocarbon structure solves the problem of aggregation fluorescence quenching of TADF materials, achieving efficient luminescence at high concentrations or solid states, with aggregation-induced luminescence enhancement characteristics and excellent TADF performance.
Patent Information
- Application Number
- CN202510532246.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-25
- Publication Date
- 2025-08-01
AI Technical Summary
Traditional TADF materials are prone to quenching of aggregated fluorescence due to intermolecular π-π stacking, and the luminescence efficiency is significantly reduced at high concentrations or solid states, and the device efficiency is severely rolled off.
Thermal activation delayed fluorescent compound designed with polysulfur aromatic hydrocarbon structure is prepared by aromatic nucleophilic substitution and condensation reaction. The compound has the characteristics of aggregation-induced luminescence enhancement, inhibits non-radiative transitions, and improves luminescence efficiency.
Maintaining efficient luminescence at high concentrations or solid states overcomes the ACQ problem of traditional TADF materials, the emission life intensity increases with the increase of temperature, and has good biocompatibility and a simple preparation method.
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Figure CN120398867A_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the technical field of thermally activated delayed fluorescence materials, and specifically relates to a polysulfur aromatic thermally activated delayed fluorescence compound and a preparation method thereof. Background Art
[0002] Thermally activated delayed fluorescence (TADF) materials can efficiently utilize triplet excitons through the reverse intersystem crossing (RISC) process, achieving an exciton utilization rate close to 100%, and have important application values in fields such as organic light-emitting diodes (OLEDs), bioimaging, and optoelectronic devices.
[0003] Traditional TADF materials usually rely on the design of donor-acceptor (D-A) molecular structures. Although they can reduce the singlet-triplet energy level difference, they are prone to the problem of aggregation-caused quenching (ACQ) of fluorescence due to intermolecular π-π stacking, and the luminescence efficiency is significantly reduced at high concentrations or in the solid state. In addition, the excited-state dynamics of most TADF materials are limited by the slow RISC process, resulting in serious device efficiency roll-off, which restricts their practical applications. Summary of the Invention
[0004] The purpose of this application is to provide a polysulfur aromatic thermally activated delayed fluorescence compound and a preparation method thereof, so as to solve the technical problems that the existing TADF materials are prone to aggregation-caused quenching of fluorescence due to intermolecular π-π stacking, the luminescence efficiency is significantly reduced at high concentrations or in the solid state, and the device efficiency roll-off is serious.
[0005] To achieve the above purpose, the first aspect of this application provides a polysulfur aromatic thermally activated delayed fluorescence compound, which has the structure shown in the following general formula 1;
[0006]
General Formula 1
[0007]
[0008] In the general formula 1, X is
[0009]
[0010] To achieve the above purpose, the second aspect of this application provides a preparation method of a polysulfur aromatic thermally activated delayed fluorescence compound, including:
[0011] Performing an aromatic nucleophilic substitution reaction on fluorosulfonylbenzene, phenothiazine, and piperidinecarboxylic acid to obtain a first intermediate product, and the first intermediate product has the structure shown in the following general formula 2 or general formula 3;
[0012] Performing a condensation reaction on the first intermediate product and a tetrasubstituted benzene with the following general formula 4 to obtain a polysulfur aromatic thermally activated delayed fluorescence compound with the following general formula 1;
[0013]
General Formula 1
[0014]
[0015]
General Formula 2
[0016]
[0017]
General Formula 3
[0018]
[0019]
General Formula 4
[0020]
[0021] Wherein, the piperidinecarboxylic acid is S-piperidinecarboxylic acid or R-piperidinecarboxylic acid, and X in the General Formula 1 is
[0022]
[0023] In one or more embodiments, the step of performing an aromatic nucleophilic substitution reaction on p-fluorosulfonylbenzene, phenothiazine and piperidinecarboxylic acid specifically is:
[0024] Dissolve phenothiazine, p-fluorosulfonylbenzene, piperidinecarboxylic acid and base a in solvent a, then heat to the first temperature, stir and react. After the reaction is completed, a solid is precipitated, filtered and washed to obtain the first intermediate product.
[0025] In one or more embodiments, the base a is NaH, K2CO3 or Cs2CO3.
[0026] In one or more embodiments, the solvent a is N,N-dimethylformamide or tetrahydrofuran.
[0027] In one or more embodiments, the first temperature is 90 - 110 °C, and the reaction time is 10 - 14 h.
[0028] In one or more embodiments, the base a is NaH, and the molar ratio of phenothiazine to base a is 1:(1.6 - 2.4).
[0029] In one or more embodiments, the molar ratio of phenothiazine, p-fluorosulfonylbenzene and piperidinecarboxylic acid is 1:(0.8 - 1.2):(0.8 - 1.2).
[0030] In one or more embodiments, the step of performing a condensation reaction on the first intermediate product and the tetrasubstituted benzene specifically is:
[0031] Dissolve the first intermediate product and the tetrasubstituted benzene in solvent b, add the condensing agent HATU, and react under an inert atmosphere. After the reaction is completed, a solid is precipitated, filtered and washed to obtain the polysulfur aromatic thermally activated delayed fluorescence compound.
[0032] In one or more embodiments, solvent b is N,N-dimethylformamide or tetrahydrofuran.
[0033] In one or more embodiments, the molar ratio of the tetrasubstituted benzene, the first intermediate product and the condensing agent HATU is 1:(4-8):(4-8).
[0034] In one or more embodiments, the reaction temperature for the reaction under an inert atmosphere is room temperature, and the reaction time is 10-14 h.
[0035] In one or more embodiments, the tetrasubstituted benzene is prepared by the following steps:
[0036] Dissolve 4-halothiophenol and hexasubstituted benzene in solvent c, add base b at the same time, and raise the temperature to the second temperature under an inert atmosphere for reaction. After the reaction is completed, a solid is precipitated, extracted and dried to obtain the tetrasubstituted benzene.
[0037] In one or more embodiments, base b is NaH, K2CO3 or Cs2CO3.
[0038] In one or more embodiments, base b is K2CO3, and the molar ratio of 4-halothiophenol, hexasubstituted benzene and base b is (1-2):(6-12):(6-15).
[0039] In one or more embodiments, the second temperature is 55-60 °C, and the reaction time is 12-24 h.
[0040] To achieve the above object, the third aspect of the present application provides an application of the polysulfur aromatic thermally activated delayed fluorescence compound described in any one of the above embodiments or the polysulfur aromatic thermally activated delayed fluorescence compound prepared by the preparation method described in any one of the above embodiments as a thermally activated delayed fluorescence material, and the thermally activated delayed fluorescence material has an aggregation-induced emission enhancement effect.
[0041] Different from the prior art, the beneficial effects of the present application are:
[0042] The polysulfur aromatic thermally activated delayed fluorescence compound of the present application exhibits a significant aggregation-induced emission enhancement effect, and the emission lifetime intensity shows an obvious increasing trend with the increase of temperature, effectively solving the problems faced by traditional TADF materials, such as fluorescence quenching in the aggregated state, significant reduction in luminescence efficiency at high concentration or in the solid state, and serious roll-off of device efficiency;
[0043] The thermally activated delayed fluorescence compound of the present application exhibits weak luminescence in a pure organic solution and shows aggregation-induced emission in an organic-aqueous mixed solution, with good biocompatibility;
[0044] The preparation method of the present application has a simple synthesis route, cheap and easily available raw materials, and is easy to commercialize on a large scale. Description of the Drawings
[0045] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.
[0046] Figure 1 It is a schematic flowchart of an embodiment of the preparation method of the thermally activated delayed fluorescence compound of the present application;
[0047] Figure 2 It is the nuclear magnetic resonance hydrogen spectrum of Luminescent Material 1 in Example 1 of the present application;
[0048] Figure 3 It is the nuclear magnetic resonance hydrogen spectrum of Luminescent Material 2 in Example 2 of the present application;
[0049] Figure 4 It is the fluorescence spectrum in Effect Example 2 of the present application;
[0050] Figure 5 It is the fluorescence emission photograph in Effect Example 2 of the present application;
[0051] Figure 6 It is the fluorescence lifetime spectrum in Effect Example 3 of the present application. Detailed Embodiments
[0052] In order to enable those skilled in the art to better understand the technical solutions in the present application, the following will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present application.
[0053] Traditional thermally activated delayed fluorescence (TADF) materials usually rely on the design of donor-acceptor (D-A) molecular structures. Although they can reduce the singlet-triplet energy gap, they often face the problem of aggregation-caused quenching (ACQ) of fluorescence, and the luminescence efficiency is significantly reduced at high concentrations or in the solid state. In addition, the excited-state dynamics of most TADF materials are limited by the slow reverse intersystem crossing (RISC) process, resulting in serious efficiency roll-off of the device, which limits their practical applications.
[0054] To solve the above problems, the applicant has developed a new type of multi-sulfur aromatic hydrocarbon thermally activated delayed fluorescence compound. Based on the multi-sulfur aromatic hydrocarbon structure, this compound exhibits aggregation-induced emission enhancement (AIE) characteristics, effectively overcomes the ACQ problem of traditional TADF materials, and has excellent TADF performance and emission lifetime intensity.
[0055] Specifically, the multi-sulfur aromatic hydrocarbon thermally activated delayed fluorescence compound of the present application has the structure shown in the following general formula 1.
[0056]
General formula 1
[0057]
[0058] In general formula 1, X is
[0059]
[0060] The thermally activated delayed fluorescence compound of the present application is based on the multi-sulfur aromatic hydrocarbon structure. Multi-sulfur aromatic hydrocarbons are a class of organic molecules with unique optoelectronic properties. The heavy-atom effect of sulfur atoms in the molecule can enhance the spin-orbit coupling (SOC), promote the reverse intersystem crossing of triplet excitons, and thus improve the TADF performance.
[0061] At the same time, the rigid conjugated backbone of multi-sulfur aromatic hydrocarbons can effectively inhibit non-radiative transitions and improve the luminescence efficiency. More importantly, multi-sulfur aromatic hydrocarbon derivatives exhibit aggregation-induced emission enhancement (AIE) characteristics, which can overcome the ACQ problem of traditional TADF materials, enabling the thermally activated delayed fluorescence compound of the present application to maintain high-efficiency luminescence under solid-state or high-concentration conditions.
[0062] The present application also provides a preparation method of the above thermally activated delayed fluorescence compound. Please refer to Figure 1 , Figure 1 is a schematic flow diagram of an implementation manner of the preparation method of the thermally activated delayed fluorescence compound of the present application.
[0063] As Figure 1 shown, the preparation method includes:
[0064] S100. Performing an aromatic nucleophilic substitution reaction on p-fluorosulfonylbenzene, phenothiazine, and piperidinecarboxylic acid to obtain a first intermediate product.
[0065] Among them, the pipecolic acid is S-pipecolic acid or R-pipecolic acid. Correspondingly, the first intermediate has the structure shown in the following General Formula 2 or General Formula 3.
[0066]
General Formula 2
[0067]
[0068]
General Formula 3
[0069]
[0070] In one embodiment, the reaction formula of S100 can be as follows:
[0071]
[0072] In one embodiment, the step of the above aromatic nucleophilic substitution reaction can be specifically:
[0073] Dissolve phenothiazine, p-fluorosulfonylbenzene, pipecolic acid and base a in solvent a, then heat to the first temperature, stir and react. After the reaction is completed, a solid is precipitated, filtered and washed to obtain the first intermediate.
[0074] In one embodiment, solvent a can be N,N-dimethylformamide or tetrahydrofuran.
[0075] In one embodiment, the first temperature can be 90-110 °C, and the reaction time can be 10-14 h.
[0076] In one embodiment, base a can be NaH, K2CO3 or Cs2CO3; specifically, when base a is NaH, the molar ratio of phenothiazine to base a can be 1:(1.6-2.4).
[0077] In one embodiment, the molar ratio of phenothiazine, p-fluorosulfonylbenzene and pipecolic acid can be 1:(0.8-1.2):(0.8-1.2).
[0078] S200. Condense the first intermediate with a tetrasubstituted benzene having General Formula 4 to obtain a multi-sulfur aromatic thermally activated delayed fluorescence compound having General Formula 1.
[0079]
General Formula 4
[0080]
[0081] In one embodiment, the step of the above condensation reaction can be specifically:
[0082] Dissolve the first intermediate product and the tetrasubstituted benzene in solvent b, add the condensing agent HATU, and react under an inert atmosphere. After the reaction is completed, a solid is precipitated, filtered and washed to obtain the polysulfur aromatic thermally activated delayed fluorescence compound.
[0083] In one embodiment, solvent b can be N,N-dimethylformamide or tetrahydrofuran.
[0084] In one embodiment, the molar ratio of the tetrasubstituted benzene, the first intermediate product and the condensing agent HATU is 1:(4-8):(4-8).
[0085] In one embodiment, the reaction temperature of the condensation reaction can be room temperature, and the reaction time can be 10-14 h.
[0086] In one embodiment, the reaction formula of the above reaction can be as follows:
[0087]
[0088] This application also provides a preparation method of the above-mentioned tetrasubstituted benzene, which specifically includes:
[0089] Dissolve 4-halothiophenol and the hexasubstituted benzene in solvent c, add base b at the same time, and heat up to the second temperature under an inert atmosphere for reaction. After the reaction is completed, a solid is precipitated, extracted and dried to obtain the tetrasubstituted benzene.
[0090] In one embodiment, base b can be NaH, K2CO3 or Cs2CO3.
[0091] In one embodiment, when base b is K2CO3, the molar ratio of 4-halothiophenol, the hexasubstituted benzene and base b can be (1-2):(6-12):(6-15).
[0092] In one embodiment, the second temperature can be 55-60 °C, and the reaction time can be 12-24 h.
[0093] Based on the preparation methods of the above embodiments, the polysulfur aromatic thermally activated delayed fluorescence compound of this application can be prepared. The synthesis route is simple, the raw materials are cheap and easy to obtain, and it is easy to commercialize on a large scale.
[0094] The effects of the technical solution of this application will be further elaborated in detail below with specific examples.
[0095] Example 1:
[0096] A polysulfur aromatic thermally activated delayed fluorescence compound - luminescent material 1 has the following structure:
[0097]
[0098] where x is
[0099] The preparation method of the luminescent material 1 is as follows:
[0100] Weigh 1 mmol of phenothiazine, 1 mmol of p-fluorosulfonylbenzene, 1 mmol of R-pipecolic acid and 2 mmol of sodium hydride, and dissolve these substances in 5.0 mL of N,N-dimethylformamide (DMF). Then, stir the reaction mixture at 100 °C overnight for about 12 hours of reaction. After the reaction is completed, pour the reaction solution into 15.0 mL of water to precipitate a solid. Vacuum filter and wash with ethanol to obtain a yellow solid, which is the first intermediate product.
[0101] Weigh 6 mmol of p-fluorothiophenol and 1 mmol of hexafluorobenzene and add them to the DMF solvent. At the same time, add 6 mmol of K2CO3 and react at 55 °C for 24 hours under a nitrogen atmosphere. After the reaction is completed, when it is cooled to room temperature, add a large amount of distilled water to produce a yellow emulsion. Add ethyl acetate to the emulsion for extraction, separate the layers, repeat three times, combine the organic phases and dry them with anhydrous sodium sulfate. Remove the solvent under reduced pressure to obtain a yellow solid. Add anhydrous ethanol to the yellow solid and stir at 50 °C for 2 hours. Cool the reaction solution to room temperature, collect the yellow solid by vacuum filtration, wash it with anhydrous ethanol, and dry the obtained solid under vacuum conditions to obtain a tetrasubstituted benzene.
[0102] Add 6 mmol of the first intermediate product and 1 mmol of the tetrasubstituted benzene to 5 mL of the DMF solvent. At the same time, add 4 mmol of O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU) and react at room temperature for 12 hours under a nitrogen atmosphere. After the reaction is completed, add water to precipitate a solid. Collect the yellow solid by vacuum filtration, wash it with anhydrous ethanol, and dry the obtained solid under vacuum conditions to obtain the target compound, that is, the luminescent material 1.
[0103] Example 2:
[0104] A polythiophene thermally activated delayed fluorescence compound - luminescent material 2 has the following structure:
[0105]
[0106] where x is
[0107] The preparation method of the luminescent material 2 is basically the same as that of Example 1, except that:
[0108] S-pipecolic acid is used to replace R-pipecolic acid in Example 1. [[ID=…]]
[0109] Example 3:
[0110] A multi-sulfur aromatic hydrocarbon thermally activated delayed fluorescence compound has the same structure as the luminescent material 1 in Example 1 and the preparation method is basically the same as that in Example 1, except that:
[0111] In the preparation process of the tetrasubstituted benzene in Example 3, 2 mmol of hexachlorobenzene and 12 mmol of p-fluorothiophenol were weighed and added to a DMF solvent, and at the same time 15 mmol of K2CO3 was added, and the reaction was carried out at 60 °C for 12 hours under a nitrogen atmosphere;
[0112] In the condensation reaction of Example 3, 8 mmol of the first intermediate product and 1 mmol of the tetrasubstituted benzene were added to 5 mL of a DMF solvent, and at the same time 8 mmol of O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU) was added, and the reaction was carried out at room temperature for 12 hours under a nitrogen atmosphere.
[0113] Effect Example 1:
[0114] 1H nuclear magnetic resonance spectrum analysis was performed on the luminescent material 1 of Example 1 and the luminescent material 2 of Example 2, and Figure 2 and Figure 3 were obtained. Figure 2 is the 1H nuclear magnetic resonance spectrum of the luminescent material 1 of Example 1 of this application, Figure 3 is the 1H nuclear magnetic resonance spectrum of the luminescent material 2 of Example 2 of this application.
[0115] As Figure 2 shown, the 1H nuclear magnetic resonance spectrum data of the luminescent material 1 are as follows, which conform to the characteristics of the target compound:
[0116] 1H NMR(500MHz,DMSO-d6)δ9.92(s,4H),7.81–7.74(m,8H),7.62(d,J=8.4Hz,8H),7.53–7.40(m,16H),7.29(tt,J=7.8,2.2Hz,8H),7.22–7.08(m,24H),7.00(dd,J=18.4,9.0Hz,8H),6.89(dd,J=23.7,8.2Hz,8H),3.78(s,4H),3.02–2.90(m,5H),2.72(s,4H),1.91(s,4H),1.72–1.52(m,9H),1.39(s,6H).
[0117] As Figure 3 shown, the 1H nuclear magnetic resonance spectrum data of the luminescent material 2 are as follows, which conform to the characteristics of the target compound:
[0118] 1H NMR(500 MHz, DMSO-d6) δ 9.91 (s, 4H), 7.81–7.74 (m, 8H), 7.62 (d, J = 8.7 Hz, 8H), 7.55–7.39 (m, 16H), 7.28 (td, J = 7.7, 1.6 Hz, 8H), 7.24–7.05 (m, 25H), 6.95 (dd, J = 34.5, 8.7 Hz, 17H), 4.02 (d, J = 13.0 Hz, 4H), 3.77 (d, J = 12.1 Hz, 4H), 2.96 (t, J = 12.1 Hz, 4H), 2.71 (d, J = 12.6 Hz, 4H), 1.90 (s, 4H), 1.72–1.34 (m, 13H).
[0119] Effect Example 2:
[0120] The luminescent material 1 of Example 1 was selected and dissolved in tetrahydrofuran (THF) to prepare a mother liquor of 10 -3 M, and then the mother liquor was diluted with a THF / water mixed solvent with different water phase volume fractions to obtain a test solution with a concentration of 10 -3 M to test the fluorescence emission intensity of the luminescent material 1 in the aggregated state. Among them, the water phase volume fractions in the THF / water mixed solvent were 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 95% respectively. The test solution was placed in a fluorescence cuvette, and its fluorescence emission behavior was observed under 365 nm laser excitation to obtain Figure 4 , Figure 4 which is the fluorescence spectrum diagram in Effect Example 2 of this application.
[0121] As Figure 4 shown, during the process of the water phase volume fraction gradually increasing from 0% to 50%, the fluorescence emission intensity of the luminescent material 1 gradually decreased. This is mainly because at low water phase ratios, the material is in a dissolved state. As the water phase increases, the solvent polarity increases, resulting in fluorescence quenching. However, as the water phase volume fraction gradually increases from 60%, the fluorescence emission intensity of the luminescent material 1 significantly increases, and the fluorescence intensity reaches the maximum value when the water phase volume fraction reaches 95%. This is mainly because when the water phase exceeds 60%, the solubility of the material drops sharply, resulting in the transformation of molecules from the dissolved state to the aggregated state, and the luminescent material 1 begins to show the effect of aggregation-induced emission enhancement.
[0122] At the same time, the luminescence photos of the test solutions with water phase volume fractions of 0%, 30%, 60%, and 90% are as Figure 5 shown, Figure 5 which is the fluorescence luminescence photo in Effect Example 2 of this application.( Figure 5 Fluorescence is difficult to distinguish after grayscale processing)
[0123] AsFigure 5 As shown, with the increase of the volume fraction of the aqueous phase, the fluorescence emission intensity of the luminescent material 1 increases significantly.
[0124] From the above experiments, it can be seen that the polythiophene thermally activated delayed fluorescence compound of Example 1 exhibits a significant aggregation-induced emission enhancement effect.
[0125] Effect Example 3:
[0126] The luminescent material 1 of Example 1 was selected and dissolved in tetrahydrofuran (THF) to prepare a 10 -5 M test solution, and the emission lifetime intensity of the test solution was measured under different temperature conditions to obtain Figure 6 , Figure 6 which is the fluorescence lifetime spectrogram in Effect Example 3 of this application.
[0127] As Figure 6 shown, with the increase of temperature, the emission lifetime intensity of the luminescent material 1 gradually increases, and the emission lifetime intensity of the luminescent material 1 shows an obvious increasing trend with the increase of temperature.
[0128] For those skilled in the art, it is obvious that this application is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of this application, this application can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of this application is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in this application. Any reference signs in the claims should not be regarded as limiting the claimed rights.
[0129] In addition, it should be understood that although this specification is described according to the embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.
Claims
1. A multi-sulfur aromatic thermally activated delayed fluorescence compound, characterized in that, It has the structure shown in the following general formula 1; [General formula 1] In the general formula 1, X is 2. A preparation method of a multi-sulfur aromatic hydrocarbon thermally activated delayed fluorescence compound, characterized in that, Including: Perfluorosulfonyl benzene, phenothiazine and piperidinecarboxylic acid are subjected to aromatic nucleophilic substitution reaction to obtain a first intermediate product, and the first intermediate product has the structure shown in the following general formula 2 or general formula 3; The first intermediate product is subjected to a condensation reaction with a tetrasubstituted benzene having the following general formula 4 to obtain a polythiophene aromatic thermally activated delayed fluorescence compound having the following general formula 1; [General formula 1] [General formula 2] [General formula 3] [General formula 4] Among them, the piperidinecarboxylic acid is S-type piperidinecarboxylic acid or R-type piperidinecarboxylic acid, and X in the general formula 1 is 3. The preparation method according to claim 2, wherein The step of subjecting perfluorosulfonyl benzene, phenothiazine and piperidinecarboxylic acid to aromatic nucleophilic substitution reaction is specifically as follows: Phenothiazine, perfluorosulfonyl benzene, piperidinecarboxylic acid and base a are dissolved in solvent a, then heated to the first temperature, stirred and reacted. After the reaction is completed, a solid is precipitated, filtered and washed to obtain the first intermediate product.
4. The preparation method according to claim 3, wherein, The base a is NaH, K2CO3 or Cs2CO3; and / or, The solvent a is N,N-dimethylformamide or tetrahydrofuran; and / or, The first temperature is 90-110 °C, and the reaction time is 10-14 h; and / or, The base a is NaH, and the molar ratio of phenothiazine to base a is 1:(1.6-2.4).
5. The preparation method according to claim 3, characterized in that, The molar ratio of phenothiazine, perfluorosulfonyl benzene and piperidinecarboxylic acid is 1:(0.8-1.2):(0.8-1.2).
6. The preparation method according to claim 2, characterized in that, The step of subjecting the first intermediate product to a condensation reaction with the tetrasubstituted benzene is specifically as follows: The first intermediate product and the tetrasubstituted benzene are dissolved in solvent b, and a condensing agent HATU is added, and the reaction is carried out under an inert atmosphere. After the reaction is completed, a solid is precipitated, filtered and washed to obtain the polythiophene aromatic thermally activated delayed fluorescence compound.
7. The preparation method according to claim 6, characterized in that, The solvent b is N,N-dimethylformamide or tetrahydrofuran; and / or, The molar ratio of the tetrasubstituted benzene, the first intermediate product and the condensing agent HATU is 1:(4-8):(4-8); and / or, The reaction temperature for the reaction under an inert atmosphere is room temperature, and the reaction time is 10-14 h.
8. The preparation method according to claim 2, characterized in that, The tetrasubstituted benzene is prepared by the following steps: 4-Halothiophenol and a hexasubstituted benzene are dissolved in solvent c, and at the same time base b is added, and the temperature is raised to the second temperature under an inert atmosphere for reaction. After the reaction is completed, a solid is precipitated, extracted and dried to obtain the tetrasubstituted benzene.
9. The preparation method according to claim 8, characterized in that, The base b is NaH, K2CO3 or Cs2CO3; and / or, The base b is K2CO3, and the molar ratio of 4-halothiophenol, hexasubstituted benzene and base b is (1-2):(6-12):(6-15); and / or, The second temperature is 55-60 °C, and the reaction time is 12-24 h.
10. Use of a multi-sulfur aromatic thermally activated delayed fluorescence compound according to claim 1 or a multi-sulfur aromatic thermally activated delayed fluorescence compound prepared by the preparation method according to any one of claims 2 to 9 as a thermally activated delayed fluorescence material, characterized in that, The thermally activated delayed fluorescence material has an aggregation-induced emission enhancement effect.