Carbonyl-terminated quinonoid compound, high-electron-mobility organic semiconductor material, and preparation method and application of carbonyl-terminated quinonoid compound and high-electron-mobility organic semiconductor material

Abstract

The invention belongs to the technical field of organic functional semiconductor materials, and particularly relates to a carbonyl-terminated quinonoid compound, a high-electron-mobility organic semiconductor material, and a preparation method and application of the carbonyl-terminated quinonoid compound and the high-electron-mobility organic semiconductor material. The invention provides a carbonyl-terminated quinonoid compound with a structure as shown in a formula I, a formula II or a formula III, which is a carbonyl-terminated condensed ring or non-condensed ring quinonoid compound and can be used as an electron-deficient acceptor unit to construct an organic semiconductor material with high electron mobility. The invention provides the preparation method of the carbonyl-terminated quinonoid compound with the structure as shown in the formula I, the formula II or the formula III, and the method provided by the invention is simple to operate and high in product yield. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of organic functional semiconductor materials, and in particular relates to a carbonyl-terminated quinone compound, a high electron mobility organic semiconductor material, and a preparation method and application thereof. Background Art

[0002] In recent years, the application of organic semiconductor materials in 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 new organic semiconductor materials with high stability, excellent transmission performance and easy processing.

[0003] To achieve this goal, organic compounds with quinone structures have become candidate materials of great interest due to their unique conjugated system, strong electron acceptor properties and stable molecular structure. However, currently, organic compounds with quinone structures generally use dicyanomethylene or indandione as end groups, which are prone to steric hindrance effects and hinder the coupling reaction at the ortho position of the end group, affecting its conjugation length and charge transfer properties, and ultimately affecting the electron mobility performance of organic semiconductor materials. Summary of the invention

[0004] The purpose of the present invention is to provide a carbonyl-terminated quinone compound, a high electron mobility organic semiconductor material, and a preparation method and application thereof. The quinone compound provided by the present invention can be used as an electron-deficient acceptor unit to construct an organic semiconductor material with high electron mobility, and the obtained organic semiconductor material shows significant advantages in electron mobility.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a carbonyl-terminated quinone compound having a structure shown in Formula I, Formula II or Formula III:

[0007]

[0008] In the formula I, formula II or formula III, R 1 are independently -H or halogen;

[0009] R 2 are independently phenylalkyl, alkyl, silyl or alkoxy;

[0010] R 3 is an aryl group;

[0011] Q is independently

[0012] X is independently O, S or Se.

[0013] Preferably, R 1 In: halogen independently includes -Cl, -Br or -I;

[0014] R 2 In: the phenylalkyl group is -PhR, and R in the phenylalkyl group is C 1 ~C 40 Straight chain alkyl or C 3 ~C 40 The alkyl group is C 1 ~C 40 Straight chain alkyl or C 3 ~C 40 Branched alkyl; the silicon group is -Si(R 1 ) 3 , the silicon-based R 1 C 1 ~C 40 Straight chain alkyl or C 3 ~C 40 The alkoxy group is -OR 2 , wherein R 2 C 1 ~C 40 Straight chain alkyl or C 3 ~C 40 Branched chain alkyl.

[0015] Preferably, the aryl group is independently phenyl, pyridyl, pyrazinyl, pyrrolyl, furyl, thiophene, selenophene, tellurophene, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, thiazo[5,4-D]thiazolyl, benzothiadiazolyl, benzoselenadiazolyl, benzotelluradiazolyl or benzotriazolyl.

[0016] Preferably, the carbonyl-terminated quinone compound is any one of the following compounds:

[0017]

[0018] The present invention provides a method for preparing the carbonyl-terminated quinone compound described in the above technical solution, comprising the following steps:

[0019] The raw material compound is subjected to a substitution reaction to obtain a methoxy compound;

[0020] The methoxy compound, hydrobromic acid and an organic solvent are mixed, and demethylation reaction and oxidation reaction are carried out in sequence to obtain R 1 The carbonyl-terminated quinone compound is -H;

[0021] The methoxy compound, the halogenation agent and the organic solvent are mixed, and demethylation reaction, oxidation reaction and halogenation reaction are carried out in sequence to obtain R 1 The carbonyl-terminated quinone compound is a halogen;

[0022] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula I, the raw material compound is any one of the following compounds:

[0023]

[0024] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula II, the raw material compound is any one of the following compounds:

[0025]

[0026] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula III, the raw material compound is:

[0027]

[0028] The present invention provides an organic semiconductor material with high electron mobility, wherein the raw materials for preparation 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.

[0029] Preferably, the preparation raw materials further include conjugated compounds; the conjugated compounds include one or more of vinyl derivatives, benzothiadiazole derivatives, pyrrolopyrrole dione derivatives, isoindigo derivatives and boron dipyrrole fluoride derivatives.

[0030] The present invention provides a method for preparing the high electron mobility organic semiconductor material described in the above technical solution, comprising the following steps:

[0031] The preparation raw materials, catalyst and organic solvent are mixed to carry out coupling reaction to obtain the organic semiconductor material with high electron mobility.

[0032] The present invention provides the use 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 an organic photoelectric device.

[0033] Preferably, the organic photoelectric device includes an organic thin film transistor, an organic thermoelectric device or an organic solar cell.

[0034] The present invention provides a carbonyl-terminated quinone compound having a structure shown in Formula I, Formula II or Formula III. The compound provided by the present invention is a carbonyl-terminated condensed ring or non-condensed ring quinone compound. The present invention helps to enhance the electron affinity of the molecule and reduce the lowest unoccupied molecular orbital (LUMO) energy level by introducing a carbonyl group at the end of the molecule, thereby improving the electron transport performance. In addition, the conjugation effect between the carbonyl group and the quinone core helps to improve the π-π stacking ability of the molecule and promote the effective transport of carriers. Therefore, compared with the use of dicyanomethylene or indandione as the end group capping, the carbonyl-terminated quinone compound provided by the present invention avoids the problem of hindering the coupling reaction at the ortho position of the end group due to the steric hindrance effect, affecting its conjugation length and charge transport properties. The carbonyl-terminated quinone compound provided by the present invention can be used as an electron-deficient acceptor unit and a variety of conjugated units to construct an organic semiconductor material with high electron mobility, and the obtained organic semiconductor material shows significant advantages in electron mobility.

[0035] At the same time, the carbonyl-terminated quinone compound provided by the present invention can further optimize its charge transfer performance and crystallinity by changing the molecular length, the electronic effect of the terminal group and the substituent. The carbonyl-terminated quinone compound provided by the present invention has high chemical stability and strong environmental adaptability, so that it has great potential in device applications, such as for n-type organic thin film transistors, bipolar transistors and photoelectric conversion devices.

[0036] The present invention provides a method for preparing the carbonyl-terminated quinone compound described in the above technical solution. Compared with the prior art, the preparation method of the present invention requires milder conditions, avoids the use of strong bases such as butyl lithium, and successfully synthesizes the carbonyl-terminated quinone compound with an amide group.

[0037] In summary, the carbonyl-terminated quinone compounds provided by the present invention have opened up a new direction for the research of high electron mobility organic semiconductor materials. The present invention optimizes its electronic structure and carrier transport path through molecular design, which can promote the practical application and development of new organic semiconductor materials in the fields of flexible electronics, optoelectronic devices, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is the H NMR spectrum of compound A1 prepared in Example 6;

[0039] Figure 2 is the H NMR spectrum of compound A2 prepared in Example 7;

[0040] Figure 3 is the H NMR spectrum of compound A3 prepared in Example 8;

[0041] Figure 4 is the H NMR spectrum of compound A4 prepared in Example 9;

[0042] Figure 5 is the H NMR spectrum of compound A5 prepared in Example 10;

[0043] Figure 6 is the H NMR spectrum of compound A6 prepared in Example 11;

[0044] Figure 7 A schematic structural diagram of an organic thin film transistor (OTFT) provided in Application Example 1;

[0045] Figure 8 The transfer characteristic curve and output characteristic curve of the OTFT device prepared in Application Example 1;

[0046] Fig. 9 A schematic diagram of the structure of an organic thermoelectric device (OTE) provided for Application Example 2;

[0047] Fig.10 The temperature-induced voltage difference curve of the OTE device prepared in Application Example 2;

[0048] In the figure: 1 is a gate electrode, 2 is an insulating layer, 3 is an organic semiconductor layer, 4 is a drain electrode, 5 is a source electrode, 6 is a substrate, and 7 is an electrode. DETAILED DESCRIPTION

[0049] The present invention provides a carbonyl-terminated quinone compound having a structure shown in Formula I, Formula II or Formula III:

[0050]

[0051] In the formula I, formula II or formula III, R 1 are independently -H or halogen;

[0052] R 2 are independently phenylalkyl, alkyl, silyl or alkoxy;

[0053] R 3 is an aryl group;

[0054] Q is independently

[0055] X is independently O, S or Se.

[0056] In the present invention, unless otherwise specified, all preparation raw materials / components are commercially available products well known to those skilled in the art.

[0057] In the present invention, R 1 In: halogen independently preferably includes -Cl, -Br or -I, more preferably -Br;

[0058] In the present invention, R 2In the phenylalkyl group, the phenylalkyl group is -PhR, and R in the phenylalkyl group can be ortho, meta or para. The phenylalkyl group R is preferably C 1 ~C 40 Straight chain alkyl or C 3 ~C 40 A branched alkyl group, more preferably C 1 ~C 30 Straight chain alkyl or C 3 ~C 30 The branched alkyl group is preferably C 1 ~C 20 Straight chain alkyl or C 3 ~C 20 The branched alkyl group is preferably C 3 ~C 20 Straight chain alkyl or C 3 ~C 20 The branched alkyl group may be -C 6 H 13 A straight chain alkyl group or a branched chain alkyl group.

[0059] In the present invention, R 2 In: The alkyl group is preferably C 1 ~C 40 Straight chain alkyl or C 3 ~C 40 Branched alkyl, more preferably C 10 ~C 40 Straight chain alkyl or C 10 ~C 40 Branched alkyl, more preferably C 20 ~C 40 Straight chain alkyl or C 20 ~C 40 Branched alkyl, in the embodiment, may be C 28 Straight chain alkyl or C 28 Branched alkyl, where C 28 The branched alkyl group is preferably:

[0060] C 28 -C in branched alkyl 12 H 25 The group is a straight chain alkyl group.

[0061] In the present invention, R 2 In: The silicon group is -Si(R 1 ) 3 , the silicon-based R 1 C 1 ~C 40 Straight chain alkyl or C 3 ~C 40A branched alkyl group, more preferably C 1 ~C 30 Straight chain alkyl or C 3 ~C 30 The branched alkyl group is preferably C 1 ~C 20 Straight chain alkyl or C 3 ~C 20 The branched alkyl group is preferably C 1 ~C 20 Straight chain alkyl or C 3 ~C 20 of branched chain alkyl.

[0062] In the present invention, R 2 In: the alkoxy group is -OR 2 , wherein R 2 C 1 ~C 40 Straight chain alkyl or C 3 ~C 40 Branched alkyl, more preferably C 1 ~C 30 Straight chain alkyl or C 3 ~C 30 The branched alkyl group is preferably C 1 ~C 20 Straight chain alkyl or C 3 ~C 20 The branched alkyl group is preferably C 1 ~C 20 Straight chain alkyl or C 3 ~C 20 of branched chain alkyl.

[0063] In the present invention, the aryl group is independently preferably phenyl, pyridyl, pyrazinyl, pyrrolyl, furyl, thiophene, selenophene, tellurophene, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, thiazo[5,4-D]thiazolyl, benzothiadiazolyl, benzoselenadiazolyl, benzotelluradiazolyl or benzotriazolyl. The R1 connected to the R3 is preferably -H or halogen, and the halogen is preferably -Cl, -Br or -I, and in the embodiment, it can be -Br.

[0064] In the present invention, the aryl group is preferably independently any one of the following groups:

[0065]

[0066] The dashed lines in the above groups indicate the attachment points of the substituents.

[0067] In the present invention, the carbonyl-terminated quinone compound may be any one of the following compounds:

[0068]

[0069] -C in Compound A2, Compound A3 and Compound A4 6 H 13 The group is a straight chain alkyl group.

[0070] -C in Compound A5 and Compound A6 12 H 25 The group is a straight chain alkyl group.

[0071] The present invention provides a method for preparing the carbonyl-terminated quinone compound described in the above technical solution, comprising the following steps:

[0072] The raw material compound is subjected to a substitution reaction to obtain a methoxy compound;

[0073] The methoxy compound, methanol, hydrobromic acid and an organic solvent (hereinafter referred to as the second organic solvent) are mixed, and demethylation reaction and oxidation reaction are carried out in sequence to obtain R 1 The carbonyl-terminated quinone compound is -H;

[0074] The methoxy compound, the halogenation agent and the organic solvent (hereinafter referred to as the third organic solvent) are mixed, and demethylation reaction, oxidation reaction and halogenation reaction are carried out in sequence to obtain R 1 The carbonyl-terminated quinone compound is a halogen;

[0075] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula I, the raw material compound is any one of the following compounds:

[0076]

[0077] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula II, the raw material compound is any one of the following compounds:

[0078]

[0079] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula III, the raw material compound is:

[0080]

[0081] The present invention provides a method for preparing the carbonyl-terminated quinone compound described in the above technical solution, using the raw material compound as For example, the preparation process is as follows:

[0082]

[0083] The present invention performs a substitution reaction on the raw material compound to obtain a methoxy compound. In the present invention, when preparing a carbonyl-terminated quinone compound having a structure shown in Formula I, the raw material compound may be the following compound:

[0084]

[0085] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula II, the raw material compound may be any one of the following compounds:

[0086]

[0087] When preparing a carbonyl-terminated quinone compound having a structure shown in Formula III, the raw material compound is any one of the following compounds:

[0088]

[0089] In the present invention, 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 is required. When the methylating agent is preferably methanol, the raw materials for the substitution reaction also include a base other than sodium methoxide.

[0090] In the present invention, when the raw material of 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 and methanol. The molar concentration of sodium methoxide in the methanol solution of sodium methoxide is preferably 5 mol / L. In the present invention, the raw material compound, the methanol solution of sodium methoxide, the catalyst and the first organic solvent are preferably mixed to carry out a substitution reaction to obtain a methoxy compound.

[0091] In the present invention, when the raw material of the substitution reaction preferably includes methanol, the present invention preferably mixes the raw material compound, methanol, a base, a catalyst and a first organic solvent to carry out a substitution reaction to obtain a methoxy compound. The base is preferably cesium carbonate.

[0092] In the present invention, the catalyst 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 the methylating agent are preferably sodium methoxide, the catalyst is cuprous chloride, and when the base is preferably cesium carbonate, the catalyst is preferably a palladium catalyst. When the catalyst is preferably cuprous chloride, the raw material for the substitution reaction preferably also includes methyl formate. The role of the methyl formate is: it can suppress the side reaction of the substitution reaction and improve the yield and purity of the current product. When the catalyst is preferably a palladium catalyst, the raw material for the substitution reaction preferably also includes tBuBrettPhos. The role of the tBuBrettPhos is: as a ligand, it can coordinate with the palladium catalyst, thereby suppressing the side reaction of the substitution reaction and improving the yield and purity of the current product.

[0093] In the present invention, when the base and the methylating agent are preferably sodium methoxide, the molar ratio of the raw material compound for preparing the substitution reaction to the sodium methoxide is preferably 1:50. The molar ratio of the raw material compound to the catalyst is preferably 1:0.1. The molar ratio of the raw 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 12h.

[0094] In the present invention, when the base is preferably cesium carbonate, the molar ratio of the raw material compound for preparing the substitution reaction to the cesium carbonate is preferably 0.5:1.5. The catalyst is preferably a palladium catalyst, and the molar ratio of the raw material compound to the palladium catalyst is preferably 0.5:0.025. The molar ratio of the raw material compound to the tBuBrettPhos is preferably 0.5:0.025. The molar ratio of the raw material compound to the methanol is preferably 0.5:5. The temperature of the substitution reaction is preferably 45-50°C, and the time is preferably 20-24h.

[0095] The first organic solvent is preferably toluene, and the toluene is preferably ultra-dry toluene. The present invention has no special requirements for the amount of the first organic solvent. The substitution reaction is carried out in a protective gas atmosphere, and the protective gas is preferably argon. The substitution reaction is carried out under stirring. After the substitution reaction is completed, the present invention preferably cools the obtained substitution reaction liquid to room temperature, and then adds a dilute hydrochloric acid solution or water to the substitution reaction liquid to quench the reaction to obtain a quenched reaction solution; the quenched reaction solution is extracted with dichloromethane, and the obtained organic phase product is dried to obtain a methoxy compound. The molar concentration of the dilute hydrochloric acid solution is preferably 1 mol / L.

[0096] After obtaining the methoxy compound, the present invention mixes the methoxy compound, hydrobromic acid and a second organic solvent, performs a demethylation reaction, and then performs an oxidation reaction to form a quinone formula to obtain R 1 The carbonyl-terminated quinone compound is -H. In the present invention, the hydrobromic acid acts as a demethylation agent. 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-proof conditions. The demethylation reaction and the oxidation reaction are preferably carried out in an air environment. The demethylation reaction and the 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, and the total time of the demethylation reaction and the oxidation is preferably 4h. After the oxidation reaction, a reaction system is obtained. In the present invention, the reaction system is preferably quenched with water to obtain a quenched reaction liquid, and the quenched reaction liquid is extracted with dichloromethane to obtain an organic phase product; the organic phase product is dried to obtain a crude product; the crude product is separated by column chromatography to obtain R 1 The carbonyl-terminated quinone compound is -H. The reagent used for the drying is anhydrous sodium sulfate. The column chromatography separation preferably uses a silica gel column, and the elution solvent is preferably dichloromethane and petroleum ether, and the volume ratio of dichloromethane and petroleum ether is preferably 1:4.

[0097] After obtaining the methoxy compound, the present invention mixes the methoxy compound, the halogenation agent and the third organic solvent, performs a demethylation reaction, then performs an oxidation reaction to form a quinone form, and finally performs a halogenation reaction to obtain R 1 The carbonyl-terminated quinone compound is a halogen. The halogenation reaction is preferably a bromination reaction. In the present invention, the halogenation reagent is preferably N-bromosuccinimide (NBS). The third organic solvent is preferably chloroform. The molar ratio of the methoxy compound and NBS is preferably 1:3-6. The demethylation reaction, oxidation reaction and halogenation reaction are all carried out under light-proof conditions. The demethylation reaction, oxidation reaction and halogenation reaction are preferably oxidized in an air environment. The demethylation reaction, oxidation and halogenation reactions are carried out sequentially at room temperature. The total time of the demethylation reaction, oxidation and halogenation reaction is preferably 30min-4h. After the halogenation reaction, a reaction system is obtained. The present invention preferably desolventizes the reaction system to obtain a crude product; the crude product is separated by column chromatography to obtain R 1 The carbonyl-terminated quinone compound is a halogen. The column chromatography separation preferably uses a silica gel column, and the elution solvent is preferably dichloromethane and petroleum ether, and the volume ratio of dichloromethane and petroleum ether is preferably 1:2-4.

[0098] The invention provides an organic semiconductor material with high electron mobility, and the raw materials for preparing the material include the carbonyl-terminated quinone compound described in the above technical solution.

[0099] In the present invention, the preparation raw materials preferably also include conjugated compounds; the conjugated compounds include one or more of vinyl derivatives, benzothiadiazole derivatives, pyrrolopyrrole dione derivatives, isoindigo derivatives and boron dipyrrole fluoride derivatives.

[0100] In the present invention, the conjugated compound is preferably any one of the following compounds:

[0101]

[0102] In the present invention, the high electron mobility organic semiconductor material preferably has any one of the following chemical structures:

[0103]

[0104] In the present invention, 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; and n in the chemical structure of the high electron mobility organic semiconductor material is 2-50.

[0105] In an embodiment of the present invention, the high electron mobility organic semiconductor material more preferably has any one of the following chemical structures:

[0106]

[0107] The n of the high electron mobility organic semiconductor material of the above chemical structure is 2-50.

[0108] The present invention provides a method for preparing the high electron mobility organic semiconductor material described in the above technical solution, comprising the following steps:

[0109] The preparation raw materials, the catalyst and the fourth organic solvent are mixed to carry out a coupling reaction to obtain the high electron mobility organic semiconductor material.

[0110] In the present invention, when the raw materials for preparation preferably include conjugated compounds, the high electron mobility organic semiconductor material is prepared by coupling reaction of the carbonyl-terminated quinone compound and the conjugated compound described in the above technical solution. The preparation method preferably includes: mixing the carbonyl-terminated quinone compound, the conjugated compound, the catalyst and the fourth organic solvent, and performing 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.

[0111] In the present invention, the catalyst preferably includes one or more of a copper catalyst, a palladium catalyst and a phosphorus catalyst, and the palladium catalyst preferably includes Pd(PPh 3 ) 4 , Pd 2 (dba) 3 and PdCl 2 The phosphorus catalyst preferably includes tri(o-tolyl)phosphine. The copper catalyst preferably includes cuprous chloride and / or cupric acetate. The fourth organic solvent preferably includes one or more of chlorobenzene (CB), toluene and dimethylacetamide (DMAc).

[0112] In the present invention, the coupling reaction is preferably carried out under heating reflux conditions, the coupling reaction temperature is preferably 120-130°C, and the time is preferably 24-48h. After the coupling reaction is completed, the present invention preferably precipitates the obtained coupling reaction solution in methanol to obtain a precipitate; the electricity-generating substance is sequentially subjected to Soxhlet extraction and purification with methanol, acetone, hexane and methyl chloride to obtain a purified substance; a chloroform solution of the purified substance is subjected to substrate treatment in methanol to obtain the high electron mobility organic semiconductor material. The chloroform preferably includes dichloromethane or chloroform (chloroform).

[0113] The present invention provides the application of the high electron mobility organic semiconductor material described in the above technical solution in an organic photoelectric device.

[0114] In the present invention, the organic photoelectric device preferably includes an organic thin film transistor, an organic thermoelectric device or an organic solar cell.

[0115] In order to further illustrate the present invention, the technical solutions provided by the present invention are described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0116] Example 1 Substitution reaction of raw material S1

[0117] This example provides the preparation of compound M1, and the reaction formula is as follows:

[0118]

[0119] 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 stirred at 115 ° C for 12 h. After cooling to room temperature, 1 M dilute hydrochloric acid solution (15 mL) was added to the obtained system to quench the reaction, and dichloromethane was used for extraction. The obtained organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the obtained filtrate was removed to obtain compound M1, which was directly used for the next step reaction.

[0120] Preparation Example 2 Substitution reaction of raw material S2

[0121] This example provides the preparation of compound M2, and the reaction formula is as follows:

[0122]

[0123] 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 stirred at 115 ° C for 12 h. After cooling to room temperature, 1 M dilute hydrochloric acid solution (15 mL) was added to the obtained system to quench the reaction, and dichloromethane was used for extraction. The obtained organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the obtained filtrate was removed to obtain compound M2, which was directly used for the next step reaction.

[0124] Preparation Example 3 Substitution reaction of raw material S4

[0125] This example provides a method for preparing compound M4, and the reaction formula is as follows:

[0126]

[0127] 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 stirred at 115 ° C for 12 h. After cooling to room temperature, 1 M dilute hydrochloric acid solution (15 mL) was added to the obtained system to quench the reaction, and dichloromethane was used for extraction. The obtained organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the obtained filtrate was removed to obtain compound M4, which was directly used for the next step reaction.

[0128] Preparation Example 4 Substitution reaction of raw material S5

[0129] This example provides a method for preparing compound M5, and the reaction formula is as follows:

[0130]

[0131] 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 stirred at 50 ° C for 20 h. After cooling to room temperature, water was added to the obtained system to quench the reaction, and dichloromethane was used for extraction. The obtained organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the obtained filtrate was removed to obtain compound M5, which was directly used for the next step reaction.

[0132] Preparation Example 5 Substitution reaction of raw material S6

[0133] This example provides a method for preparing compound M6, and the reaction formula is as follows:

[0134]

[0135] In an argon atmosphere, compound S6 (705 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 stirred at 50 ° C for 20 h. After cooling to room temperature, water was added to the obtained system to quench the reaction, and dichloromethane was used for extraction. The obtained organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent in the obtained filtrate was removed to obtain compound M6, which was directly used for the next step reaction.

[0136] Example 6R 1 Reaction of Br

[0137] This embodiment provides a method for preparing compound A1, and the reaction formula is as follows:

[0138]

[0139] 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 three times. The reaction was carried out at room temperature in the dark for 30 min (this process includes demethylation, oxidation and bromination). After the reaction, the solvent was removed and the crude product was separated by silica gel column (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 4) to obtain compound A1 as a brown solid (yield 73 mg, yield 21%).

[0140] 1 HNMR (800 MHz, DMSO) δ7.72 (s, 2H). MALDI-TOF (m / z): calculated value is 345.830, measured value is 345.831; the H NMR spectrum of compound A1 is as follows Figure 1 shown.

[0141] Example 7R 1 The reaction of H

[0142] This embodiment provides a method for preparing compound A2, and the reaction formula is as follows:

[0143]

[0144] 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 thereto. The reaction was stirred at 90°C for 4 h and cooled to room temperature. Water was added to the obtained system to quench the reaction. Dichloromethane was used for extraction, and the obtained organic phase was dried over anhydrous sodium sulfate and filtered to remove the solvent from the obtained filtrate. The obtained crude product was separated by silica gel column (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 4) to obtain compound A2 as a brown solid (yield 300 mg, yield 64%).

[0145] 1 H NMR (400 MHz, CDCl3) δ7.12 (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 is 936.497, measured value is 936.502; the H NMR spectrum of compound A2 is shown in Figure 2 shown.

[0146] Example 8R 1 Reaction of Br

[0147] This embodiment provides a method for preparing compound A3, and the reaction formula is as follows:

[0148]

[0149] 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 three times. The reaction was carried out at room temperature in the dark for 30 min. After the reaction, the solvent was removed and the crude product was separated by a silica gel column (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 4) to obtain compound A3 as a reddish brown solid (yield 307 mg, yield 56%).

[0150] 1 H NMR (400 MHz, CDCl3) δ7.20-7.14 (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 is 1094.316, measured value is 1094.310; the H NMR spectrum of compound A3 is shown in Figure 3 shown.

[0151] Example 9R 1 Reaction of Br

[0152] This embodiment provides a method for preparing compound A4, and the reaction formula is as follows:

[0153]

[0154] 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 three times. The reaction was carried out at room temperature in the dark for 30 min. After the reaction, the solvent was removed and the crude product was separated by silica gel column (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 4) to obtain compound A4 as a reddish brown solid (yield 260 mg, yield 45%).

[0155] 1 H NMR (400 MHz, CDCl3) δ7.22-7.04 (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 is 1156.245, measured value is 1156.251; the H NMR spectrum of compound A4 is shown in Figure 4 shown.

[0156] Example 10R 1 Reaction of Br

[0157] This embodiment provides a method for preparing compound A5, and the reaction formula is as follows:

[0158]

[0159] 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 three times. The reaction was carried out at room temperature in the dark for 4 h. After the reaction, the solvent was removed and the crude product was separated by silica gel column (the eluent used was dichloromethane / petroleum ether (v:v) = 1 / 2) to obtain compound A5 as a dark blue solid (yield 194 mg, yield 27%).

[0160] 1 H NMR (400 MHz, CDCl3) δ9.95 (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 is 1436.648, measured value is 1436.657; the H NMR spectrum of compound A5 is shown in Figure 5 shown.

[0161] Example 11R 1 Reaction of Br

[0162] This embodiment provides a method for preparing compound A6, and the reaction formula is as follows:

[0163]

[0164] 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 three times. The reaction was carried out at room temperature in the dark for 30 min. After the reaction, the solvent was removed and the crude product was separated by silica gel column (the eluent used was dichloromethane / petroleum ether (v:v) = 2 / 1) to obtain compound A6 as a reddish brown solid (yield 147 mg, yield 23%).

[0165] 1 H NMR (400 MHz, CDCl3) δ10.10 (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 is 1280.819, measured value is 1280.823; the H NMR spectrum of compound A6 is shown in Figure 6 shown.

[0166] Example 12 Copolymerization

[0167] This embodiment provides a method for preparing a polymer PBT, and the reaction formula is as follows:

[0168]

[0169] 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 bottle, 10 mL of ultra-dry chlorobenzene was added to dissolve, and then lyophilized with liquid nitrogen to deoxygenate, and Pd(PPh 3 ) 4 (9 mg, 0.008 mmol), reacted at 130°C reflux for 48 h, after the reaction, the obtained product system was precipitated in methanol, and the obtained precipitate was purified by Soxhlet extraction with methanol, acetone, hexane and dichloromethane in sequence, the obtained polymer was dissolved in hot chlorobenzene and poured into methanol for precipitation, the solid material was collected by filtration, and the polymer PBT (87%) was obtained. Gel permeation chromatography (GPC): Mn = 66.9 kDa,

[0170] Example 13 Copolymerization

[0171] This embodiment provides a method for preparing the polymer PQTDPPO-TVT, and the reaction formula is as follows:

[0172]

[0173] 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 bottle, 2 mL of ultra-dry toluene was added to dissolve, and then lyophilized with liquid nitrogen to deoxygenate. Pd 2 (dba) 3 (3.7 mg, 0.004 mmol), tri(o-tolyl)phosphine (4.9 mg, 0.016 mmol), react at 120°C reflux for 48 hours; after the reaction, the obtained product system is precipitated in methanol, and the obtained precipitate is purified by Soxhlet extraction with methanol, acetone, hexane and chloroform in sequence, the obtained chloroform solution is concentrated and poured into methanol for precipitation, and the solid material is collected by filtration to obtain the polymer PQTDPPO-TVT (85%). Gel permeation chromatography (GPC): Mn = 29.5 kDa,

[0174] Example 14 Self-polymerization

[0175] This embodiment provides a method for preparing the polymer PQTDPPO-Tz, and the reaction formula is as follows:

[0176]

[0177] In an argon atmosphere, compound A6 (200 mg, 0.16 mmol) was added to a 10 mL Shrek bottle, 2 mL of ultra-dry chlorobenzene and 0.2 mL of ultra-dry DMAc were added to dissolve, and then lyophilized with liquid nitrogen to deoxygenate, and PdCl was added. 2 (2.8 mg, 0.016 mmol), cuprous chloride (3.2 mg, 0.032 mmol), cupric acetate (87 mg, 0.48 mmol), react at 120°C reflux for 48 h; after the reaction, the obtained product system is precipitated in methanol, and the obtained precipitate is purified by Soxhlet extraction with methanol, acetone, hexane and chloroform in sequence, the obtained chloroform solution is concentrated and poured into methanol for precipitation, and the solid material is collected by filtration to obtain the polymer PQTDPPO-Tz (81%). Gel permeation chromatography (GPC): Mn = 14.5 kDa,

[0178] Application Example 1

[0179] Organic thin film transistors (OTFTs) were prepared using the polymer PQTDPPO-TVT prepared in Example 13 of the present invention and the polymer PQTDPPO-Tz prepared in Example 14 as semiconductor materials, respectively. The schematic diagram of the structure is shown in FIG. Figure 7 As shown, the specific steps are as follows:

[0180] The preparation process was completed in a glove box with an argon atmosphere. A silicon wafer with a 300nm thick silicon dioxide layer on the surface was used as a substrate, and a 35nm thick gold (Au) layer was prepared on the substrate by vacuum evaporation as a source / drain electrode; polymers PQTDPPO-TVT and PQTDPPO-Tz were dissolved in o-dichlorobenzene to obtain polymer PQTDPPO-TVT and PQTDPPO-Tz solutions with a concentration of 4mg / mL, and the polymers PQTDPPO-TVT and PQTDPPO-Tz were spin-coated on different substrates with source / drain electrodes by a spin coater, the spin coater speed was 1000rpm, and the spin coating time was 90s. After the spin coating, a thermal annealing treatment was performed at 150° C. for 10 min, and then the organic semiconductor layer was cooled to room temperature to obtain a organic semiconductor layer; a PMMA layer with a thickness of 600 nm was prepared on the surface of the organic semiconductor layer by a spin coating method as an insulating layer, and then a 90 nm thick aluminum (Al) layer was prepared on the surface of the insulating layer by a vacuum evaporation method as a gate to obtain an OTFT device.

[0181] Figure 8Table 1 is the transfer characteristic curve and output characteristic curve of the OTFT device prepared in Application Example 1, and Table 2 is the performance parameters of the OTFT device prepared in Application Example 1. The results show that the OTFT device prepared by using the polymers PQTDPPO-TVT and PQTDPPO-Tz in the present invention as the active layer has excellent electron mobility.

[0182] Table 1 Performance measurement results of OTFT devices prepared in Application Example 1

[0183]

[0184]

[0185] Application Example 2

[0186] The polymer PBT prepared in Example 12 of the present invention is used as a semiconductor material to prepare an organic thermoelectric device (OTE), the structural schematic diagram of which is shown in FIG. Fig. 9 As shown, the specific steps are as follows:

[0187] The preparation process is completed in a glove box with an argon atmosphere. The substrate used is a glass sheet. First, a 32nm thick gold (Au) is prepared on the substrate by vacuum evaporation as the electrode of the OTE device. The polymer PBT in the present invention is selected as the organic semiconductor layer material, and a chlorobenzene solution of PBT is prepared with a concentration of 4mg / mL. It is fully dissolved at room temperature and mixed with different volumes of N-DMBI chlorobenzene solution with a concentration of 4mg / mL for 30 minutes (in order to obtain OTE devices with different doping ratios). The rotation speed of the spin coater is 1000rpm, and the spin coating time is 120 seconds. Afterwards, the semiconductor layer is thermally annealed at an annealing temperature of 150°C and an annealing time of 60 minutes to obtain an OTE device.

[0188] Fig.10 2 is a temperature-induced voltage difference curve of the OTE device prepared in Application Example 2, and Table 2 is the performance parameters of the OTE device prepared in Application Example 2. The results show that the OTE device prepared using the polymer PBT in the present invention 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.

[0189] Table 2 Performance test results of OTE devices prepared in Application Example 2

[0190] Doping ratio (mol%) 30 40 50 Conductivity (S / cm) 41.5 105.4 50.6 Seebeck coefficient (μV / K) 98.9 57.5 56.8

[0191] From the above embodiments, it can be seen that the present invention provides a carbonyl-terminated quinone compound having a structure shown in Formula I, Formula II or Formula III. The compound provided by the present invention is a carbonyl-terminated condensed ring or non-condensed ring quinone compound. The present invention helps to enhance the electron affinity of the molecule and reduce the lowest unoccupied molecular orbital (LUMO) energy level by introducing a carbonyl group at the end of the molecule, thereby improving the electron transport performance. In addition, the conjugation effect between the carbonyl group and the quinone core helps to improve the π-π stacking ability of the molecule and promote the effective transport of carriers. Therefore, compared with the use of dicyanomethylene or indandione as the end group capping, the carbonyl-terminated quinone compound provided by the present invention avoids the problem of the existence of a steric hindrance effect that hinders the coupling reaction at the ortho position of the end group, affecting its conjugation length and charge transport properties. The carbonyl-terminated quinone compound provided by the present invention can be used as an electron-deficient acceptor unit and a variety of conjugated units to construct an organic semiconductor material with high electron mobility, and the resulting organic semiconductor material shows significant advantages in electron mobility.

[0192] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A carbonyl-terminated quinone compound, characterized in that: It has the structure shown in Formula I, Formula II or Formula III: In the formula I, formula II or formula III, R1 is independently -H or halogen; R2 is independently phenylalkyl, alkyl, silicon or alkoxy; R3 is an aryl group; Q is independently X is independently O, S or Se.

2. The carbonyl-terminated quinone compound according to claim 1, characterized in that In R1: halogen independently includes -Cl, -Br or -I; In R2: the phenylalkyl group is -PhR, and R in the phenylalkyl group is C1-C 40 Straight chain alkyl or C3~C 40 The alkyl group is C1~C 40 Straight chain alkyl or C3~C 40 Branched alkyl; the silicon group is -Si(R 1 )3, wherein R 1 C1~C 40 Straight chain alkyl or C3~C 40 The alkoxy group is -OR 2 , wherein R 2 C1~C 40 Straight chain alkyl or C3~C 40 Branched chain alkyl.

3. The carbonyl-terminated quinone compound according to claim 1, characterized in that The aryl group is independently phenyl, pyridyl, pyrazinyl, pyrrolyl, furyl, thiophene, selenophene, tellurophene, imidazolyl, thiazolyl, 1,3,4-thiadiazolyl, thiazolo[5,4-D]thiazolyl, benzothiadiazolyl, benzoselenadiazolyl, benzotelluradiazolyl or benzotriazolyl.

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

5. The method for preparing a carbonyl-terminated quinone compound according to any one of claims 1 to 4, characterized in that: The following steps are involved: The raw material compound is subjected to a substitution reaction to obtain a methoxy compound; The methoxy compound, hydrobromic acid and an organic solvent are mixed, and demethylation reaction and oxidation reaction are sequentially performed to obtain the carbonyl-terminated quinone compound in which R1 is -H; The methoxy compound, the halogenation agent and the organic solvent are mixed, and demethylation reaction, oxidation reaction and halogenation reaction are carried out in sequence to obtain the carbonyl-terminated quinone compound in which R1 is a halogen; When preparing a carbonyl-terminated quinone compound having a structure shown in Formula I, the raw material compound is any one of the following compounds: When preparing a carbonyl-terminated quinone compound having a structure shown in Formula II, the raw material compound is any one of the following compounds: When preparing a carbonyl-terminated quinone compound having a structure shown in Formula III, the raw material compound is:

6. A high electron mobility organic semiconductor material, characterized in that: The preparation raw materials include the carbonyl-terminated quinone compound according to any one of claims 1 to 4 or the carbonyl-terminated quinone compound prepared by the preparation method according to claim 5.

7. The high electron mobility organic semiconductor material according to claim 6, characterized in that: The preparation raw materials also include conjugated compounds; the conjugated compounds include one or more of vinyl derivatives, benzothiadiazole derivatives, pyrrolopyrrole dione derivatives, isoindigo derivatives and boron dipyrrole fluoride derivatives.

8. The method for preparing the high electron mobility organic semiconductor material according to claim 6 or 7, characterized in that: The following steps are involved: The preparation raw materials, catalyst and organic solvent are mixed to carry out coupling reaction to obtain the organic semiconductor material with high electron mobility.

9. Use of the high electron mobility organic semiconductor material according to claim 6 or 7 or the high electron mobility organic semiconductor material prepared by the preparation method according to claim 8 in an organic photoelectric device.

10. The use according to claim 9, characterized in that: The organic photoelectric device includes an organic thin film transistor, an organic thermoelectric device or an organic solar cell.

Images