Carbonyl-terminated quinonoid compound, and high-electron-mobility organic semiconductor material and preparation method therefor and use thereof

Abstract

A carbonyl-terminated quinonoid compound having a structure as represented by formula I, formula II or formula III, and a high-electron-mobility organic semiconductor material constructed by using same as an electron-deficient acceptor unit, and a preparation method therefor and the use thereof. The method provided by the present application is simple to operate and has a high product yield.

Description

A carbonyl-terminated quinone compound, a high electron mobility organic semiconductor material, its preparation method and application Technical Field

[0001] This application belongs to the field of organic functional semiconductor materials technology, specifically relating to a carbonyl-terminated quinone compound, a high electron mobility organic semiconductor material, its preparation method and application. Background Technology

[0002] In recent years, the application of organic semiconductor materials in fields such as organic thin-film transistors (OTFTs), organic photovoltaic cells (OPVs), organic light-emitting diodes (OLEDs), and flexible electronic devices has attracted widespread attention. Among them, organic semiconductor materials with high electron mobility have become one of the core research directions, especially in the development of novel organic semiconductor materials with high stability, excellent electron transport performance, and ease of processing.

[0003] For this goal, organic compounds with quinone structures have become promising candidate materials due to their unique conjugated system, strong electron acceptor properties, and stable molecular structure. However, current organic compounds with quinone structures generally use dicyanomethylene or indanedione as end groups for capping, which easily leads to steric hindrance effects that hinder coupling reactions at the ortho-position of the end groups, affecting their conjugation length and charge transport properties, and ultimately impacting the electron mobility performance of organic semiconductor materials. Summary of the Invention

[0004] The purpose of this application is to provide a carbonyl-terminated quinone compound, a high electron mobility organic semiconductor material, a preparation method thereof, and its application. The quinone compound provided in this application can be used as an electron-deficient acceptor unit to construct an organic semiconductor material with high electron mobility, and the resulting organic semiconductor material exhibits a significant advantage in electron mobility.

[0005] To achieve the above objectives, this application provides the following technical solution:

[0006] This application provides a carbonyl-terminated quinone compound having the structure shown in Formula I, Formula II, or Formula III:

[0007] In Formula I and Formula II or Formula III, R1 is independently -H or a halogen;

[0008] R2 is independently phenylalkyl, alkyl, silyl or alkoxy;

[0009] R3 is an aryl group;

[0010] Q independently for

[0011] X can be O, S, or Se independently.

[0012] Preferably, in R1: the halogen includes -Cl, -Br or -I;

[0013] In R2: the phenyl alkyl group is -PhR, and R in the phenyl alkyl group is C1 to C2. 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups; the alkyl group is C1 to C2. 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups; the silicon group is -Si(R 1 )3, R in the silicon-based 1 For C1~C 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups; the alkoxy group is -OR 2 R in the alkoxy group 2 C1~C 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups.

[0014] Preferably, the aryl group is independently phenyl, pyridyl, pyrazinyl, pyrroleyl, furanyl, thiophenyl, selenophenyl, telluryl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, thiazo[5,4-D]thiazolyl, benzothiadiazolyl, benzoselenodiazolyl, benzotelluric acid diazolyl, or benzotriazolyl.

[0015] Preferably, the carbonyl-terminated quinone compound is any one of the following compounds:

[0016] This application provides a method for preparing the carbonyl-terminated quinone compound described in the above technical solution, comprising the following steps:

[0017] The starting compound is subjected to a substitution reaction to obtain methoxy compounds;

[0018] The methoxy compound, hydrobromic acid, and organic solvent are mixed and subjected to demethylation and oxidation reactions in sequence to obtain the carbonyl-terminated quinone compound with R1 being -H.

[0019] The methoxy compound, the halogenating agent, and the organic solvent are mixed and subjected to demethylation, oxidation, and halogenation reactions in sequence to obtain the carbonyl-terminated quinone compound with R1 as a halogen.

[0020] When preparing a carbonyl-terminated quinone compound having the structure shown in Formula I, the starting compound is any one of the following compounds:

[0021] When preparing carbonyl-terminated quinone compounds having the structure shown in Formula II, the starting compound is any one of the following compounds:

[0022] When preparing a carbonyl-terminated quinone compound having the structure shown in Formula III, the starting compound is:

[0023] This application provides an organic semiconductor material with high electron mobility, the raw materials for which include the carbonyl-terminated quinone compound described in the above technical solution or the carbonyl-terminated quinone compound prepared by the preparation method described in the above technical solution.

[0024] Preferably, the raw materials for preparation also include conjugated compounds; the conjugated compounds include one or more of the following: ethylene derivatives, benzothiadiazole derivatives, pyrrolopyrrole dione derivatives, isoindigo derivatives, and boron fluoride dipyrrole derivatives.

[0025] This application provides a method for preparing the high electron mobility organic semiconductor material described in the above technical solution, including the following steps:

[0026] The raw materials, catalyst, and organic solvent are mixed and coupled to obtain the high electron mobility organic semiconductor material.

[0027] This application provides the application of the high electron mobility organic semiconductor material described in the above technical solution or the high electron mobility organic semiconductor material prepared by the preparation method described in the above technical solution in organic optoelectronic devices.

[0028] Preferably, the organic optoelectronic device includes an organic thin-film transistor, an organic thermoelectric device, or an organic solar cell.

[0029] This application provides a carbonyl-terminated quinone compound having the structure shown in Formula I, Formula II, or Formula III. The compound provided is a carbonyl-terminated fused-ring or non-fused-ring quinone compound. By introducing a carbonyl group at the molecule's end, this application helps enhance the molecule's electron affinity and lower the lowest unoccupied molecular orbital (LUMO) energy level, thereby improving electron transport performance. Furthermore, the conjugation effect between the carbonyl group and the quinone core helps improve the molecule's π-π stacking ability, promoting efficient carrier transport. Therefore, compared to using dicyanomethylene or indanedione as the end-capping group, the carbonyl-terminated quinone compound provided in this application avoids the problem of steric hindrance hindering coupling reactions at the ortho-position of the end group, thus affecting its conjugation length and charge transport properties. The carbonyl-terminated quinone compound provided in this application can serve as an electron-deficient acceptor unit and, together with various conjugated units, construct organic semiconductor materials with high electron mobility. The resulting organic semiconductor materials exhibit significant advantages in electron mobility.

[0030] Meanwhile, the carbonyl-terminated quinone compounds provided in this application can further optimize their charge transport performance and crystallinity by changing the molecular length, terminal groups, and electronic effects of substituents. The carbonyl-terminated quinone compounds provided in this application exhibit high chemical stability and strong environmental adaptability, making them highly promising for device applications, such as n-type organic thin-film transistors, bipolar transistors, and optoelectronic conversion devices.

[0031] This application provides a method for preparing carbonyl-terminated quinone compounds as described above. Compared with the prior art, the preparation method described in this application requires milder conditions, avoids the use of strong bases such as butyllithium, and successfully synthesizes carbonyl-terminated quinone compounds with amide groups.

[0032] In summary, the carbonyl-terminated quinone compounds provided in this application open up new directions for the research of organic semiconductor materials with high electron mobility. By optimizing their electronic structure and carrier transport pathways through molecular design, this application can promote the practical application and development of novel organic semiconductor materials in fields such as flexible electronics and optoelectronic devices. Attached Figure Description

[0033] Figure 1 shows the 1H NMR spectrum of compound A1 obtained in Example 6;

[0034] Figure 2 shows the 1H NMR spectrum of compound A2 obtained in Example 7;

[0035] Figure 3 shows the 1H NMR spectrum of compound A3 obtained in Example 8;

[0036] Figure 4 shows the 1H NMR spectrum of compound A4 obtained in Example 9;

[0037] Figure 5 shows the 1H NMR spectrum of compound A5 obtained in Example 10;

[0038] Figure 6 shows the 1H NMR spectrum of compound A6 obtained in Example 11;

[0039] Figure 7 is a schematic diagram of the structure of the organic thin-film transistor (OTFT) provided in Application Example 1;

[0040] Figure 8 shows the transfer characteristic curves and output characteristic curves of the OTFT device prepared in Application Example 1;

[0041] Figure 9 is a schematic diagram of the structure of the organic thermoelectric device (OTE) provided in Application Example 2;

[0042] Figure 10 is a temperature-induced voltage difference curve of the OTE device prepared in Application Example 2;

[0043] In the diagram: 1 is the gate electrode, 2 is the insulating layer, 3 is the organic semiconductor layer, 4 is the drain electrode, 5 is the source electrode, 6 is the substrate, and 7 is the electrode. Detailed Implementation

[0044] This application provides a carbonyl-terminated quinone compound having the structure shown in Formula I, Formula II, or Formula III:

[0045] In Formula I and Formula II or Formula III, R1 is independently -H or a halogen;

[0046] R2 is independently phenylalkyl, alkyl, silyl or alkoxy;

[0047] R3 is an aryl group;

[0048] Q independently for

[0049] X can be O, S, or Se independently.

[0050] Unless otherwise specified, all raw materials / components used in this application are commercially available products well known to those skilled in the art.

[0051] In this application, in R1: the halogen independently preferably includes -Cl, -Br or -I, more preferably -Br;

[0052] In this application, R2 refers to a benzyl alkyl group, which is -PhR, and R in the benzyl alkyl group can be ortho, meta, or para. R in the benzyl alkyl group is preferably C1 to C2. 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups, more preferably C1 to C2, are preferred. 30 Straight-chain alkyl or C3-C 30 Branched alkyl groups, more preferably C1 to C2. 20 Straight-chain alkyl or C3-C 20 Branched alkyl groups, most preferably C3-C4 20 Straight-chain alkyl or C3-C 20 Branched alkyl groups, in the examples, can be -C6H. 13 Straight-chain alkyl or branched alkyl.

[0053] In this application, R2: the alkyl group is preferably C1 to C2. 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups, more preferably C14-24-3 ... 10 ~C 40 straight-chain alkyl or C 10 ~C 40 Branched alkyl groups, more preferably C 20 ~C 40 straight-chain alkyl or C 20 ~C 40 Branched alkyl groups, which in the examples can be C18-284 ... 28straight-chain alkyl or C 28 Branched alkyl groups, wherein C 28 Branched alkyl groups are preferably:

[0054] C 28 -C in branched alkyl groups 12 H 25 The group is a straight-chain alkyl group.

[0055] In this application, R2: the silicon-based material is -Si(R 1 )3, R in the silicon-based 1 C1~C 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups, more preferably C1 to C2, are preferred. 30 Straight-chain alkyl or C3-C 30 Branched alkyl groups, more preferably C1 to C2. 20 Straight-chain alkyl or C3-C 20 Branched alkyl groups, most preferably C1 to C2. 20 Straight-chain alkyl or C3-C 20 Branched alkyl groups.

[0056] In this application, R2: the alkoxy group is -OR 2 R in the alkoxy group 2 C1~C 40 Straight-chain alkyl or C3-C 40 Branched alkyl groups, more preferably C1 to C1, are preferred. 30 Straight-chain alkyl or C3-C 30 Branched alkyl groups, more preferably C1 to C2. 20 Straight-chain alkyl or C3-C 20 Branched alkyl groups, most preferably C1 to C2. 20 Straight-chain alkyl or C3-C 20 Branched alkyl groups.

[0057] In this application, the aryl group is independently preferably phenyl, pyridyl, pyrazinyl, pyrroleyl, furanyl, thiophenyl, selenophenyl, telluryl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, thiazo[5,4-D]thiazolyl, benzothiadiazolyl, benzoselenodiazolyl, benzotelluric acid diazolyl, or benzotriazolyl. The R1 attached to R3 is preferably -H or a halogen, and the halogen is preferably -Cl, -Br, or -I; in the examples, it can be -Br.

[0058] In this application, the aryl group is preferably any one of the following groups:

[0059] The dashed lines in the above groups indicate the connection sites of substituents.

[0060] In this application, the carbonyl-terminated quinone compound can be any of the following compounds:

[0061] The -C6H in compounds A2, A3, and A4 13 The group is a straight-chain alkyl group.

[0062] -C in compounds A5 and A6 12 H 25 The group is a straight-chain alkyl group.

[0063] This application provides a method for preparing the carbonyl-terminated quinone compound described in the above technical solution, comprising the following steps:

[0064] The starting compound is subjected to a substitution reaction to obtain methoxy compounds;

[0065] The methoxy compound, methanol, hydrobromic acid and an organic solvent (hereinafter referred to as the second organic solvent) are mixed and subjected to demethylation and oxidation reactions in sequence to obtain the carbonyl-terminated quinone compound with R1 being -H;

[0066] The methoxy compound, the halogenating agent, and the organic solvent (hereinafter referred to as the third organic solvent) are mixed and subjected to demethylation, oxidation, and halogenation reactions in sequence to obtain the carbonyl-terminated quinone compound with R1 as a halogen.

[0067] When preparing a carbonyl-terminated quinone compound having the structure shown in Formula I, the starting compound is any one of the following compounds:

[0068] When preparing carbonyl-terminated quinone compounds having the structure shown in Formula II, the starting compound is any one of the following compounds:

[0069] When preparing a carbonyl-terminated quinone compound having the structure shown in Formula III, the starting compound is:

[0070] This application provides a method for preparing the carbonyl-terminated quinone compound described in the above technical solution, using the aforementioned raw material compound as... For example, the preparation process is as follows:

[0071] This application involves subjecting a starting compound to a substitution reaction to yield a methoxylated compound. In this application, when preparing a carbonyl-terminated quinone compound having the structure shown in Formula I, the starting compound can be one of the following compounds:

[0072] When preparing carbonyl-terminated quinone compounds having the structure shown in Formula II, the starting compound can be any of the following compounds:

[0073] When preparing a carbonyl-terminated quinone compound having the structure shown in Formula III, the starting compound is any one of the following compounds:

[0074] In this application, the substitution reaction is carried out in a first organic solvent. The raw materials for the substitution reaction preferably also include a catalyst. The raw materials for the substitution reaction preferably also include a base and a methylating agent. The methylating agent is preferably methanol or sodium methoxide. When the methylating agent is preferably sodium methoxide, the sodium methoxide is used as both a methylating agent and a base in the substitution reaction, and no additional base needs to be added. When the methylating agent is preferably methanol, the raw materials for the substitution reaction also include a base other than sodium methoxide.

[0075] In this application, when the starting material for the substitution reaction preferably includes sodium methoxide, the sodium methoxide is preferably used in the form of a methanol solution of sodium methoxide. The methanol solution of sodium methoxide is obtained by reacting metallic sodium with methanol. The molar concentration of sodium methoxide in the methanol solution of sodium methoxide is preferably 5 mol / L. In this application, the starting material compound, the methanol solution of sodium methoxide, the catalyst, and a first organic solvent are preferably mixed to carry out the substitution reaction to obtain a methoxylated compound.

[0076] In this application, when the raw materials for the substitution reaction preferably include methanol, the raw material compound, methanol, base, catalyst, and a first organic solvent are preferably mixed to carry out the substitution reaction to obtain a methoxylated compound. The base is preferably cesium carbonate.

[0077] The catalyst described in this application preferably includes cuprous chloride (CuCl) and / or a palladium catalyst, more preferably cuprous chloride or a palladium catalyst. The palladium catalyst can be tBuBrettPhos Pd G3. When the base and methylating agent are preferably sodium methoxide, the catalyst is cuprous chloride; when the base is preferably cesium carbonate, the catalyst is preferably a palladium catalyst. When the catalyst is preferably cuprous chloride, the raw materials for the substitution reaction preferably also include methyl formate. The role of methyl formate is to suppress the side reactions of the substitution reaction and improve the yield and purity of the current product. When the catalyst is preferably a palladium catalyst, the raw materials for the substitution reaction preferably also include tBuBrettPhos. The role of tBuBrettPhos is to act as a ligand to coordinate with the palladium catalyst, thereby suppressing the side reactions of the substitution reaction and improving the yield and purity of the current product.

[0078] In this application, when the base and methylating agent are preferably sodium methoxide, the molar ratio of the starting material compound to the sodium methoxide in the substitution reaction is preferably 1:50. The molar ratio of the starting material compound to the catalyst is preferably 1:0.1. The molar ratio of the starting material compound to the methyl formate is preferably 1:1. The temperature of the substitution reaction is preferably 110–115°C, and the time is preferably 12 h.

[0079] In this application, when the base is preferably cesium carbonate, the molar ratio of the starting compound to cesium carbonate in the substitution reaction is preferably 0.5:1.5. The catalyst is preferably a palladium catalyst, and the molar ratio of the starting compound to the palladium catalyst is preferably 0.5:0.025. The molar ratio of the starting compound to tBuBrettPhos is preferably 0.5:0.025. The molar ratio of the starting compound to methanol is preferably 0.5:5. The temperature of the substitution reaction is preferably 45–50°C, and the time is preferably 20–24 hours.

[0080] The first organic solvent is preferably toluene, and the toluene is preferably ultra-dry toluene. This application does not have specific requirements regarding the amount of the first organic solvent. The substitution reaction is carried out under a protective gas atmosphere, preferably argon. The substitution reaction is carried out under stirring. After the substitution reaction is completed, this application preferably cools the obtained substitution reaction solution to room temperature, and then adds a dilute hydrochloric acid solution or water to the substitution reaction solution to quench the reaction, obtaining a quenched reaction solution; the quenched reaction solution is extracted with dichloromethane, and the resulting organic phase product is dried to obtain a methoxylated compound. The molar concentration of the dilute hydrochloric acid solution is preferably 1 mol / L.

[0081] After obtaining the methoxy compound, this application mixes the methoxy compound, hydrobromic acid, and a second organic solvent to carry out a demethylation reaction, followed by an oxidation reaction to form a quinone compound with R1 being -H, resulting in the carbonyl-terminated quinone compound. In this application, the hydrobromic acid acts as a demethylation reagent. The second organic solvent is preferably tetrahydrofuran. The mass percentage of the hydrobromic acid is preferably 48%. The demethylation reaction is carried out under light-protected conditions. The demethylation reaction and the oxidation reaction are preferably carried out in air. The demethylation reaction and oxidation are carried out sequentially. The temperature of the demethylation reaction is preferably 90°C, and the demethylation reaction is carried out under stirring. The temperature of the oxidation reaction is preferably 90°C, and the oxidation reaction is carried out under stirring. The total time for the demethylation reaction and oxidation is preferably 4 hours. Following the oxidation reaction, a reaction system is obtained. Preferably, the reaction system is quenched with water to obtain a quenching reaction solution. The quenching reaction solution is then extracted with dichloromethane to obtain an organic phase product. The organic phase product is dried to obtain a crude product. The crude product is then subjected to column chromatography to obtain the carbonyl-terminated quinone compound with R1 being -H. The drying reagent is limited to anhydrous sodium sulfate. The column chromatography separation preferably uses a silica gel column, and the eluent is preferably dichloromethane and petroleum ether, with a preferred volume ratio of 1:4.

[0082] After obtaining the methoxy compound, this application mixes the methoxy compound, a halogenating reagent, and a third organic solvent to perform a demethylation reaction, followed by an oxidation reaction to form a quinone, and finally a halogenation reaction to obtain the carbonyl-terminated quinone compound with R1 as a halogen. The halogenation reaction is preferably a bromination reaction. In this application, the halogenating reagent is preferably N-bromosuccinimide (NBS). The third organic solvent is preferably chloroform. The molar ratio of the methoxy compound to NBS is preferably 1:3 to 6. The demethylation, oxidation, and halogenation reactions are all carried out under light-protected conditions. The demethylation, oxidation, and halogenation reactions are preferably carried out in air. The demethylation, oxidation, and halogenation reactions are carried out sequentially at room temperature. The total time for the demethylation, oxidation, and halogenation reactions is preferably 30 min to 4 h. After the halogenation reaction, a reaction system is obtained. This application preferably removes the solvent from the reaction system to obtain a crude product; the crude product is then separated by column chromatography to obtain the carbonyl-terminated quinone compound with R1 as a halogen. The column chromatography separation preferably uses a silica gel column, and the elution solvent is preferably dichloromethane and petroleum ether, with the volume ratio of dichloromethane to petroleum ether preferably being 1:2 to 4.

[0083] This application provides an organic semiconductor material with high electron mobility, the raw materials for which include the carbonyl-terminated quinone compound described in the above technical solution.

[0084] In this application, the raw materials preferably also include conjugated compounds; the conjugated compounds include one or more of the following: ethylene derivatives, benzothiadiazole derivatives, pyrrolopyrrole dione derivatives, isoindigo derivatives, and boron fluoride dipyrrole derivatives.

[0085] In this application, the conjugated compound is preferably any one of the following compounds:

[0086] In this application, the high electron mobility organic semiconductor material preferably has any one of the following chemical structures:

[0087] In this application, the A group in the chemical structure of the high electron mobility organic semiconductor material is the corresponding group when the conjugated compound forms the high electron mobility organic semiconductor material; n in the chemical structure of the high electron mobility organic semiconductor material is 2 to 50.

[0088] In embodiments of this application, the high electron mobility organic semiconductor material more preferably has any one of the following chemical structures:

[0089] The n of the high electron mobility organic semiconductor material with the above chemical structure is 2 to 50.

[0090] This application provides a method for preparing the high electron mobility organic semiconductor material described in the above technical solution, including the following steps:

[0091] The raw materials, catalyst, and fourth organic solvent are mixed and coupled to obtain the high electron mobility organic semiconductor material.

[0092] In this application, when the raw materials preferably include a conjugated compound, the high electron mobility organic semiconductor material is prepared by a coupling reaction between the carbonyl-terminated quinone compound and the conjugated compound as described in the above technical solution. The preparation method preferably includes: mixing the carbonyl-terminated quinone compound, the conjugated compound, a catalyst, and a fourth organic solvent, and carrying out a coupling reaction to obtain the high electron mobility organic semiconductor material. The molar ratio of the carbonyl-terminated quinone compound to the conjugated compound is preferably 1:1.

[0093] In this application, the catalyst preferably comprises one or more of copper catalysts, palladium catalysts, and phosphorus catalysts. The palladium catalyst preferably comprises one or more of Pd(PPh3)4, Pd2(dba)3, and PdCl2. The phosphorus catalyst preferably comprises tris(o-tolyl)phosphine. The copper catalyst preferably comprises cuprous chloride and / or copper acetate. The fourth organic solvent preferably comprises one or more of chlorobenzene (CB), toluene, and dimethylacetamide (DMAc).

[0094] In this application, the coupling reaction is preferably carried out under reflux conditions, with the temperature preferably being 120–130°C and the time preferably being 24–48 hours. After the coupling reaction is completed, the resulting coupling reaction solution is preferably precipitated in methanol to obtain a precipitate; the precipitate is then purified by Soxhlet extraction sequentially with methanol, acetone, hexane, and chloromethane to obtain a purified product; and a chloroform solution of the purified product is then placed in methanol as a substrate to obtain the high electron mobility organic semiconductor material. The chloromethane preferably includes dichloromethane or chloroform.

[0095] This application provides the application of the high electron mobility organic semiconductor material described in the above technical solution in organic optoelectronic devices.

[0096] In this application, the organic optoelectronic device preferably includes an organic thin-film transistor, an organic thermoelectric device, or an organic solar cell.

[0097] To further illustrate this application, the technical solutions provided by this application are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of this application.

[0098] Example 1 Substitution reaction of raw material S1

[0099] This embodiment provides the preparation of compound M1, and the reaction formula is shown below:

[0100] In an argon atmosphere, compound S1 (316 mg, 1 mmol), cuprous chloride (10 mg, 0.1 mmol), methyl formate (60 mg, 1 mmol), and sodium methoxide (5 M methanol solution, 10 mL, 50 mmol) were dissolved in 10 mL of ultra-dry toluene, and the mixture was stirred at 115 °C for 12 h. After cooling to room temperature, the reaction was quenched by adding 1 M dilute hydrochloric acid solution (15 mL), and the mixture was extracted with dichloromethane. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the filtrate was removed to obtain compound M1, which was directly added to the next reaction step.

[0101] Preparation Example 2: Substitution reaction of raw material S2

[0102] This embodiment provides the preparation of compound M2, and the reaction formula is shown below:

[0103] In an argon atmosphere, compound S2 (1.065 g, 1 mmol), cuprous chloride (10 mg, 0.1 mmol), methyl formate (60 mg, 1 mmol), and sodium methoxide (5 M methanol solution, 10 mL, 50 mmol) were dissolved in 10 mL of ultra-dry toluene, and the mixture was stirred at 115 °C for 12 h. After cooling to room temperature, the reaction was quenched by adding 1 M dilute hydrochloric acid solution (15 mL), and the mixture was extracted with dichloromethane. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the filtrate was removed to obtain compound M2, which was directly added to the next reaction step.

[0104] Preparation Example 3: Substitution reaction of raw material S4

[0105] This embodiment provides a method for preparing compound M4, and the reaction formula is shown below:

[0106] In an argon atmosphere, compound S4 (1.127 g, 1 mmol), cuprous chloride (10 mg, 0.1 mmol), methyl formate (60 mg, 1 mmol), and sodium methoxide (5 M methanol solution, 10 mL, 50 mmol) were dissolved in 10 mL of ultra-dry toluene, and the mixture was stirred at 115 °C for 12 h. After cooling to room temperature, the reaction was quenched by adding 1 M dilute hydrochloric acid solution (15 mL), and the mixture was extracted with dichloromethane. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the filtrate was removed to obtain compound M4, which was then directly added to the next reaction step.

[0107] Preparation Example 4: Substitution reaction of raw material S5

[0108] This embodiment provides a method for preparing compound M5, and the reaction formula is shown below:

[0109] In an argon atmosphere, compound S5 (704 mg, 0.5 mmol), tBuBrettPhos Pd G3 (21 mg, 0.025 mmol), tBuBrettPhos (12 mg, 0.025 mmol), cesium carbonate (488 mg, 1.5 mmol), and methanol (0.2 mL, 5 mmol) were dissolved in 10 mL of ultra-dry toluene, and the mixture was stirred at 50 °C for 20 h. After cooling to room temperature, the reaction was quenched with water, and the mixture was extracted with dichloromethane. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the filtrate was removed to obtain compound M5, which was directly added to the next reaction step.

[0110] Preparation Example 5: Substitution reaction of raw material S6

[0111] This embodiment provides a method for preparing compound M6, and the reaction formula is shown below:

[0112] In an argon atmosphere, compound S6 (705 mg, 0.5 mmol), tBuBrettPhos PdG3 (21 mg, 0.025 mmol), tBuBrettPhos (12 mg, 0.025 mmol), cesium carbonate (488 mg, 1.5 mmol), and methanol (0.2 mL, 5 mmol) were dissolved in 10 mL of ultra-dry toluene, and the mixture was stirred at 50 °C for 20 h. After cooling to room temperature, the reaction was quenched with water, and the mixture was extracted with dichloromethane. The resulting organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the filtrate was removed to obtain compound M6, which was then directly added to the next reaction step.

[0113] Example 6: Reaction of R1 with Br

[0114] This embodiment provides a method for preparing compound A1, and the reaction formula is shown below:

[0115] In an air atmosphere, compound M1 (218 mg, 1 mmol) was dissolved in 20 mL of chloroform, and NBS (534 mg, 3 mmol) was added in three portions. The reaction was carried out at room temperature in the dark for 30 min (this process included demethylation, oxidation, and bromination). After the reaction was completed, the solvent was removed, and the crude product was separated by silica gel column chromatography (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 4) to give compound A1 as a brown solid (yield of 73 mg, yield of 21%).

[0116] 1 1H NMR (800MHz, DMSO) δ 7.72 (s, 2H). MALDI-TOF (m / z): calculated value 345.830, measured value 345.831; the 1H NMR spectrum of compound A1 is shown in Figure 1.

[0117] Example 7: Reaction of R1 with H

[0118] This embodiment provides a method for preparing compound A2, and the reaction formula is shown below:

[0119] In an air atmosphere, compound M2 (484 mg, 0.5 mmol) was dissolved in 10 mL of tetrahydrofuran, and then hydrobromic acid (48 wt.% aqueous solution, 5 mL) was added. The mixture was stirred at 90 °C for 4 h, cooled to room temperature, and the reaction was quenched with water. The mixture was extracted with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate. The solvent in the filtrate was removed by filtration. The crude product was separated by silica gel column chromatography (using dichloromethane / petroleum ether (v:v) = 1 / 4 as the eluent) to give compound A2 as a brown solid (yield 300 mg, yield 64%).

[0120] 1 1H NMR (400MHz, CDCl3) δ 7.12 (m, 16H), 6.77 (s, 2H), 6.06 (s, 2H), 2.59 (t, 8H), 1.59 (m, 8H), 1.34–1.27 (m, 24H), 0.86 (t, 12H). MALDI-TOF (m / z): calculated value 936.497, measured value 936.502; the 1H NMR spectrum of compound A2 is shown in Figure 2.

[0121] Example 8: Reaction of R1 with Br

[0122] This embodiment provides a method for preparing compound A3, and the reaction formula is shown below:

[0123] In an air atmosphere, compound M2 (484 mg, 0.5 mmol) was dissolved in 10 mL of chloroform, and NBS (267 mg, 1.5 mmol) was added in three portions. The reaction was carried out at room temperature in the dark for 30 min. After the reaction was completed, the solvent was removed, and the crude product was separated by silica gel column chromatography (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 4) to give compound A3 as a reddish-brown solid (yield of 307 mg, yield of 56%).

[0124] 1 1H NMR (400MHz, CDCl3) δ 7.20–7.14 (m, 16H), 6.78 (s, 2H), 2.60 (t, 8H), 1.66–1.59 (m, 8H), 1.30 (m, 24H), 0.85 (t, 12H). MALDI-TOF (m / z): calculated value 1094.316, measured value 1094.310; The 1H NMR spectrum of compound A3 is shown in Figure 3.

[0125] Example 9: Reaction of R1 with Br

[0126] This embodiment provides a method for preparing compound A4, and the reaction formula is shown below:

[0127] In an air atmosphere, compound M4 (515 mg, 0.5 mmol) was dissolved in 10 mL of chloroform, and NBS (267 mg, 1.5 mmol) was added in three portions. The reaction was carried out at room temperature in the dark for 30 min. After the reaction was completed, the solvent was removed, and the crude product was separated by silica gel column chromatography (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 4) to give compound A4, which was a reddish-brown solid (yield of 260 mg, yield of 45%).

[0128] 1 1H NMR (400MHz, CDCl3) δ 7.22–7.04 (m, 16H), 2.59 (t, 8H), 1.59 (m, 8H), 1.33–1.26 (m, 25H), 0.87 (t, 12H). MALDI-TOF (m / z): calculated value 1156.245, measured value 1156.251; the 1H NMR spectrum of compound A4 is shown in Figure 4.

[0129] Example 10: Reaction of R1 with Br

[0130] This embodiment provides a method for preparing compound A5, and the reaction formula is shown below:

[0131] In an air atmosphere, compound M5 (655 mg, 0.5 mmol) was dissolved in 20 mL of chloroform, and NBS (534 mg, 3 mmol) was added in three portions. The reaction was carried out at room temperature in the dark for 4 h. After the reaction was completed, the solvent was removed, and the crude product was separated by silica gel column chromatography (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 2) to give compound A5 as a dark blue solid (yield of 194 mg, yield of 27%).

[0132] 1 1H NMR (400MHz, CDCl3) δ 9.95 (s, 2H), 7.61 (d, 2H), 7.09 (d, 2H), 4.03 (t, 4H), 1.69 (m, 4H), 1.24 (m, 94H), 0.87 (t, 12H). MALDI-TOF (m / z): calculated value 1436.648, measured value 1436.657; the 1H NMR spectrum of compound A5 is shown in Figure 5.

[0133] Example 11: Reaction where R1 is H

[0134] This embodiment provides a method for preparing compound A6, and the reaction formula is shown below:

[0135] In an air atmosphere, compound M6 (656 mg, 0.5 mmol) was dissolved in 10 mL of chloroform, and NBS (267 mg, 1.5 mmol) was added in three portions. The reaction was carried out at room temperature in the dark for 30 min. After the reaction was completed, the solvent was removed, and the crude product was separated by silica gel column chromatography (the eluent used was dichloromethane / petroleum ether (v:v) = 2 / 1) to give compound A6 as a reddish-brown solid (yield of 147 mg, yield of 23%).

[0136] 1 1H NMR (400MHz, CDCl3) δ 10.10 (s, 2H), 8.92 (s, 2H), 8.66 (s, 2H), 4.05 (t, 4H), 1.70 (m, 4H), 1.23 (m, 94H), 0.87 (t, 12H). MALDI-TOF (m / z): calculated value 1280.819, measured value 1280.823; The 1H NMR spectrum of compound A6 is shown in Figure 6.

[0137] Example 12 Copolymer

[0138] This embodiment provides a method for preparing polymer PBT, and the reaction formula is shown below:

[0139] In an argon atmosphere, compound A1 (64 mg, 0.17 mmol) and compound TII (201 mg, 0.17 mmol) were added to a 50 mL Shrek flask, dissolved in 10 mL of ultra-dry chlorobenzene, and then lyophilized in liquid nitrogen to remove oxygen. Pd(PPh3)4 (9 mg, 0.008 mmol) was added, and the mixture was refluxed at 130 °C for 48 h. After the reaction, the resulting product system was precipitated in methanol, and the precipitate was purified by Soxhlet extraction with methanol, acetone, hexane, and dichloromethane. The resulting polymer was dissolved in hot chlorobenzene and then precipitated in methanol. The solid material was collected by filtration to obtain polymer PBT (87%). Gel permeation chromatography (GPC): Mn = 66.9 kDa, D = 1.6.

[0140] Example 13 Copolymer

[0141] This embodiment provides a method for preparing the polymer PQTDPPO-TVT, and the reaction formula is shown below:

[0142] In an argon atmosphere, compound A5 (144 mg, 0.1 mmol) and trans-1,2-bis(tributyltin)ethylene (61 mg, 0.1 mmol) were added to a 10 mL Shrek flask, dissolved in 2 mL of ultra-dry toluene, then lyophilized in liquid nitrogen to remove oxygen. Pd2(dba)3 (3.7 mg, 0.004 mmol) and tris(o-tolyl)phosphine (4.9 mg, 0.016 mmol) were added, and the mixture was reacted at 120 °C under reflux for 48 h. After the reaction, the resulting product system was precipitated in methanol, and the precipitate was purified by Soxhlet extraction with methanol, acetone, hexane, and chloroform. The chloroform solution was concentrated and then precipitated in methanol. The solid material was collected by filtration to obtain polymer PQTDPPO-TVT (85%). Gel permeation chromatography (GPC): Mn = 29.5 kDa.

[0143] Example 14 Self-polymerization

[0144] This embodiment provides a method for preparing the polymer PQTDPPO-Tz, and the reaction formula is shown below:

[0145] Compound A6 (200 mg, 0.16 mmol) was added to a 10 mL Shrek flask under an argon atmosphere, dissolved in 2 mL of ultra-dry chlorobenzene and 0.2 mL of ultra-dry DMAc, then lyophilized in liquid nitrogen to remove oxygen. PdCl2 (2.8 mg, 0.016 mmol), cuprous chloride (3.2 mg, 0.032 mmol), and copper acetate (87 mg, 0.48 mmol) were added, and the mixture was refluxed at 120 °C for 48 h. After the reaction, the resulting product system was precipitated in methanol, and the precipitate was purified by Soxhlet extraction with methanol, acetone, hexane, and chloroform. The chloroform solution was concentrated and then precipitated in methanol. The solid material was collected by filtration to obtain polymer PQTDPPO-Tz (81%). Gel permeation chromatography (GPC): Mn = 14.5 kDa.

[0146] Application Example 1

[0147] Organic thin-film transistors (OTFTs) were fabricated using the polymer PQTDPPO-TVT prepared in Example 13 and the polymer PQTDPPO-Tz prepared in Example 14 as semiconductor materials, respectively. The structural schematic diagram is shown in Figure 7. The specific steps are as follows:

[0148] The preparation process was completed in a glove box under an argon atmosphere. A silicon wafer with a 300 nm thick silicon dioxide layer on its surface was used as the substrate. A 35 nm thick gold (Au) layer was prepared on the substrate using vacuum evaporation as the source / drain electrode. Polymers PQTDPPO-TVT and PQTDPPO-Tz were dissolved in o-dichlorobenzene to obtain polymer solutions with a concentration of 4 mg / mL. The polymer solutions PQTDPPO-TVT and PQTDPPO-Tz were then spin-coated onto different substrates with source / drain electrodes using a spin coater at a speed of 1000 rpm for 90 s. After spin coating, the organic semiconductor layer was subjected to thermal annealing at 150°C for 10 minutes and then cooled to room temperature. A PMMA layer with a thickness of 600 nm was prepared on the surface of the organic semiconductor layer by spin coating as an insulating layer. Then, an aluminum (Al) layer with a thickness of 90 nm was prepared on the surface of the insulating layer by vacuum evaporation as a gate to obtain an OTFT device.

[0149] Figure 8 shows the transfer characteristic curves and output characteristic curves of the OTFT device prepared in Application Example 1, and Table 1 shows the performance parameters of the OTFT device prepared in Application Example 1. The results show that the OTFT device prepared using the polymers PQTDPPO-TVT and PQTDPPO-Tz in this application as active layers has excellent electron mobility.

[0150] Table 1. Performance measurement results of the OTFT device prepared in Application Example 1

[0151] Application Example 2

[0152] Organic thermoelectric devices (OTEs) were fabricated using the polymer PBT prepared in Example 12 of this application as semiconductor materials. The structural schematic diagram is shown in Figure 9. The specific steps are as follows:

[0153] The fabrication process was completed in an argon-atmospheric glove box. A glass substrate was used, and a 32 nm thick layer of gold (Au) was first deposited on the substrate using vacuum evaporation to serve as the electrode for the OTE device. The polymer PBT described in this application was selected as the organic semiconductor layer material. A chlorobenzene solution of PBT with a concentration of 4 mg / mL was prepared, fully dissolved at room temperature, and mixed with different volumes of 4 mg / mL N-DMBI chlorobenzene solution for 30 minutes (to obtain OTE devices with different doping ratios). The spin coater was used at 1000 rpm for 120 seconds. The semiconductor layer was then thermally annealed at 150°C for 60 minutes to obtain the OTE device.

[0154] Figure 10 shows the temperature-induced voltage difference curve of the OTE device prepared in Application Example 2, and Table 2 shows the performance parameters of the OTE device prepared in Application Example 2. The results show that the OTE device prepared using the polymer PBT of this application as the charge transport layer has excellent device performance. The doping ratio in Table 2 is the molar ratio of N-DMBI and polymer PBT in the organic semiconductor layer.

[0155] Table 2 Performance test results of the OTE device prepared in Application Example 2

[0156] As can be seen from the above embodiments, this application provides a carbonyl-terminated quinone compound having the structure shown in Formula I, Formula II, or Formula III. The compound provided in this application is a carbonyl-terminated fused-ring or non-fused-ring quinone compound. By introducing a carbonyl group at the molecule's end, this application helps to enhance the molecule's electron affinity and lower the lowest unoccupied molecular orbital (LUMO) energy level, thereby improving electron transport performance. Furthermore, the conjugation effect between the carbonyl group and the quinone core helps to improve the molecule's π-π stacking ability, promoting efficient carrier transport. Therefore, compared with using dicyanomethylene or indanedione as the end-capping group, the carbonyl-terminated quinone compound provided in this application avoids the problem of steric hindrance hindering the coupling reaction at the ortho position of the end group, thus affecting its conjugation length and charge transport properties. The carbonyl-terminated quinone compound provided in this application can serve as an electron-deficient acceptor unit and, together with various conjugated units, construct organic semiconductor materials with high electron mobility. The resulting organic semiconductor materials exhibit significant advantages in electron mobility.

[0157] Although the above embodiments have provided a detailed description of this application, they are only some embodiments of this application, not all embodiments. Other embodiments can be obtained based on these embodiments without creative intent, and these embodiments all fall within the protection scope of this application.

Claims

1. A carbonyl-terminated quinoidal compound, characterized by, having the structure of Formula I, Formula II, or Formula III: R1independently is -H or halogen in the formula I and the formula II or the formula III; R2independently is phenylalkyl, alkyl, silicon-based or alkoxy; R3is aryl; Q is independently X independently is O, S or Se.

2. The carbonyl-terminated quinoidal compound according to claim 1, wherein Halogen in R1includes -Cl, -Br or -I. R2: said phenylalkyl is -PhR, said phenylalkyl having R as C1-C 40 linear alkyl or C3-C 40 branched alkyl; said alkyl is C1-C 40 linear alkyl or C3-C 40 branched alkyl; said silyl is -Si(R 1 )3, said silyl having R 1 as C1-C 40 linear alkyl or C3-C 40 branched alkyl; said alkoxy is -OR 2 , said alkoxy having R 2 as C1-C 40 linear alkyl or C3-C 40 branched alkyl.

3. The carbonyl-terminated quinoidal compound according to claim 1, wherein The aryl independently is phenyl, pyridyl, pyrazinyl, pyrrolyl, furanyl, thienyl, selenophenyl, tellurolphenyl, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, thiazolo[5,4-D]thiazolyl, benzothiadiazolyl, benzoselelndiazolyl, benzotellurindiazolyl or benzotriazolyl.

4. The carbonyl-terminated quinonoid compound according to any one of claims 1 to 3, characterized in that, The carbonyl-terminated quinonoid compound is any one of the following compounds:

5. A process for the preparation of a carbonyl-terminated quinonoid compound according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: The starting compound is subjected to a substitution reaction to obtain a methoxy compound; The methoxy compound is mixed with hydrobromic acid and an organic solvent, and subjected to a demethylation reaction and an oxidation reaction in sequence to obtain the carbonyl-terminated quinone formula compound with R1 being -H; The methoxy compound is mixed with a halogenating agent and an organic solvent, and subjected to a demethylation reaction, an oxidation reaction and a halogenation reaction in sequence to obtain the carbonyl-terminated quinone formula compound with R1 being halogen; When preparing a carbonyl-terminated quinone compound having the structure shown in Formula I, the starting compound is any one of the following compounds: When preparing a carbonyl-terminated quinone compound having the structure shown in Formula II, the starting compound is any one of the following compounds: When preparing a carbonyl-terminated quinone compound having the structure shown in Formula III, the starting compound is:

6. The production method according to claim 5, wherein The starting material of the substitution reaction further comprises a base and a methylating agent, and the methylating agent is methanol or sodium methoxide. The starting material of the substitution reaction further comprises a catalyst, and the catalyst comprises cuprous chloride and / or a palladium catalyst.

7. The preparation method according to claim 5, characterized in that, After the substitution reaction, the obtained substitution reaction solution is cooled to room temperature, and dilute hydrochloric acid solution or water is added to the cooled substitution reaction solution to quench the reaction, thereby obtaining a quenching reaction solution; the quenching reaction solution is extracted with dichloromethane to obtain an organic phase product, and the organic phase product is dried to obtain the methoxy compound.

8. The preparation method according to claim 5, characterized in that, After the oxidation reaction, the obtained oxidation reaction system is quenched with water to obtain a quenching reaction solution, and the quenching reaction solution is extracted with dichloromethane to obtain an organic phase; the organic phase is dried to obtain a crude product; the crude product is subjected to column chromatography separation to obtain the carbonyl-terminated quinone formula compound with R1 being -H; the column chromatography separation uses a silica gel column, and the elution solvent is dichloromethane and petroleum ether.

9. The preparation method according to claim 5, characterized in that, The halogenating agent is N-bromosuccinimide, and the molar ratio of the methoxy compound to N-bromosuccinimide is 1:3-6.

10. The production method according to claim 5 or 9, characterized by, After the halogenation reaction, the obtained halogenation reaction system is desolvated to obtain a crude product; the crude product is subjected to column chromatography separation to obtain the carboxyl-terminated quinone formula compound with R1 being halogen; the column chromatography separation uses a silica gel column, and the elution solvent is dichioromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether is 1:2-4.

11. A high electron mobility organic semiconductor material, characterized in that, The starting material comprises the carbonyl-terminated quinone formula compound of any one of claims 1-4 or the carbonyl-terminated quinone formula compound prepared by the preparation method of any one of claims 5-10.

12. The high-mobility organic semiconductor material of claim 11, wherein, The starting material further comprises a conjugated compound; the conjugated compound comprises one or more of ethylene derivatives, benzothiadiazole derivatives, diketopyrrolopyrrole derivatives, isatin derivatives and fluorinated boron dipyrromethene derivatives.

13. The high-mobility organic semiconductor material of claim 12, wherein, The conjugate compound is any one of the following compounds:

14. The high-mobility organic semiconductor material of claim 11, wherein, The high-mobility organic semiconductor material has any one of the following chemical structures: n is 2-50.

15. Process for the production of a high-mobility organic semiconductor material according to any one of claims 11 to 14, characterized in that The method comprises the following steps: The preparation raw material, the catalyst and the organic solvent are mixed to carry out a coupling reaction, so as to obtain the high electron mobility organic semiconductor material.

16. The method of claim 15, wherein, When the preparation raw material comprises a conjugated compound, the molar ratio of the carbonyl-terminated quinoid compound and the conjugated compound is 1:

1.

17. The preparation method according to claim 15, characterized in that, The catalyst comprises one or more of copper catalyst, palladium catalyst and phosphorus catalyst.

18. The method of claim 15, wherein, The temperature of the coupling reaction is 120-130°C, and the time is 24-48h.

19. The application of the high electron mobility organic semiconductor material of any one of claims 11-14 or the high electron mobility organic semiconductor material prepared by the preparation method of any one of claims 15-18 in an organic optoelectronic device.

20. The use according to claim 19, characterized in that, The organic optoelectronic device comprises an organic thin film transistor, an organic thermoelectric device or an organic solar cell.

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