Sulfuryl-containing organic semiconductor material as well as preparation method and application thereof

Abstract

The invention discloses an organic semiconductor material containing a sulfuryl structure as shown in a formula (I) as well as a preparation method and application of the organic semiconductor material. According to the invention, a bromine-substituted sulfuryl-containing condensed ring structure is taken as a substrate, substituent groups are reasonably selected, and the organic semiconductor material with strong luminescence characteristic as shown in the formula (I) is prepared through Suzuki coupling reaction. The organic semiconductor material containing the sulfuryl structure has typical bipolar electrical characteristics, and has practical application value in the organic electronics fields of organic light-emitting diodes, organic field effect transistors, organic light-emitting transistors and the like.

Description

Technical Field

[0001] The invention belongs to the field of organic semiconductors, and specifically comprises a class of organic semiconductor materials containing sulfone groups, and a preparation method and application thereof. Background Art

[0002] Organic semiconductor materials are the foundation of the development of organic electronics. Due to their advantages such as rich structures and adjustable properties, they have attracted widespread attention from researchers. After years of development, organic semiconductors have been widely used in fields such as organic field effect transistors (OFETs) and organic light-emitting diodes (OLEDs). Among them, high-mobility luminescent organic semiconductors are a type of material that has both high carrier mobility and strong solid-state luminescence properties, and have great application potential in the fields of organic light-emitting transistors (OLETs) and organic electrically pumped lasers (OEPLs). However, the strong π-π interaction required for high-mobility materials usually produces fluorescence quenching in the solid state, resulting in weak luminescence properties of the material in the solid state. Designing high-mobility strong luminescent semiconductor materials is very challenging. After development, some high-mobility strong luminescent semiconductor materials with excellent performance have been reported, but they still cannot meet the needs. In particular, the reported material systems are mainly p-type materials, and n-type and bipolar materials are very scarce. Since electrons and holes need to be injected and transported simultaneously during device operation, bipolarity is crucial to achieving high-performance devices. In summary, designing and exploring bipolar organic light-emitting semiconductor materials is a key issue that needs to be solved in the field. Summary of the invention

[0003] In order to solve the problem of lack of high-performance bipolar light-emitting organic semiconductor materials, the present invention provides an organic semiconductor material containing a sulfone group structure represented by formula (I), and a preparation method and application thereof.

[0004] The present invention provides an organic semiconductor material containing a sulfone group structure represented by formula (I):

[0005]

[0006] Wherein, M is a core unit selected from the following sulfone-containing structures:

[0007]

[0008] A is independently selected from S, Se;

[0009] represents the attachment site of the group;

[0010] R 1 , R 2 are the same or different and are each independently selected from the following aryl groups or heteroaryl groups:

[0011]

[0012] R 3 are the same or different, each independently selected from H, halogen, cyano, C 1-20 Alkyl, halogen substituted C 1-20 Alkyl; n is selected from any natural number between 0 and 10.

[0013] According to an embodiment of the present invention, R 3 Substitution may be at any of the above mentioned aryl or heteroaryl groups.

[0014] According to an embodiment of the present invention, n is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0015] According to an embodiment of the present invention, C 1-20 Alkyl groups include C 1-20 Straight chain alkyl or C 1-20 Branched chain alkyl.

[0016] According to an embodiment of the present invention, C 1-20 Alkyl is C 1-12 Alkyl, further C 1-6 Alkyl, for example tert-butyl.

[0017] According to an embodiment of the present invention, M is A is selected from S and Se.

[0018] According to an embodiment of the present invention, R 1 With R 2 Same, selected from the following groups:

[0019]

[0020] According to an embodiment of the present invention, R 3 The same or different, each independently selected from H, C 1-6 alkyl.

[0021] According to an embodiment of the present invention, the light-emitting organic semiconductor material containing a sulfone structure represented by formula (I) is represented by formula (II):

[0022]

[0023] A is selected from S and Se;

[0024] R 3 are the same or different, each independently selected from H, halogen, cyano, C 1-20 Alkyl, halogen substituted C 1-20 alkyl;

[0025] n is selected from any natural number between 0 and 10;

[0026] Preferably, R 3 same;

[0027] Preferably, R 3 Selected from H, C 1-12 Alkyl (e.g. C 1-6 alkyl, such as tert-butyl);

[0028] Preferably, n is selected from any natural number between 0-3.

[0029] The present invention also provides a method for preparing the organic semiconductor material containing a sulfone group structure represented by the above formula (I), the preparation method comprising the following steps:

[0030] 1) a compound containing a core unit of a sulfone structure undergoes a bromine substitution reaction to obtain a bromine substituted product;

[0031] 2) The bromine-substituted product obtained in step 1) is subjected to a Suzuki coupling reaction with an aryl boronic acid or a heteroaryl boronic acid (or an aryl boronic acid pinacol ester or a heteroaryl boronic acid pinacol ester) to obtain an organic semiconductor material containing a sulfone group structure as shown in formula (I).

[0032] The present invention also provides a method for preparing the organic semiconductor material containing a sulfone group structure represented by the above formula (II), the preparation method comprising the following steps:

[0033] 1) Compound 1 containing a core unit of a sulfone structure undergoes a bromine substitution reaction to obtain a bromine substituted product 2;

[0034] The reaction formula is as follows:

[0035]

[0036] 2) the bromine-substituted product 2 obtained in step 1) is subjected to a Suzuki coupling reaction with an aryl boronic acid or an aryl boronic acid pinacol ester to obtain an organic semiconductor material containing a sulfone group structure represented by formula (II);

[0037] The reaction formula is as follows:

[0038]

[0039] In the formula, A, R 3 , n has the same meaning as described above in formula (II).

[0040] According to an embodiment of the present invention, in the method for preparing the organic semiconductor material containing a sulfone structure represented by the above formula (I) and / or formula (II),

[0041] In step 1), the bromination reagent is NBS;

[0042] And / or, in step 1), concentrated sulfuric acid is added to the reaction system;

[0043] And / or, the reaction temperature in step 1) is room temperature;

[0044] and / or, step 2) is carried out under an inert gas (e.g., argon) atmosphere;

[0045] And / or, step 2) the reaction solvent is toluene;

[0046] And / or, the catalyst for the reaction in step 2) is tetrakistriphenylphosphine palladium;

[0047] And / or, step 2) adding potassium carbonate to the reaction system; preferably, the concentration of the potassium carbonate solution is 2 mol / L; further preferably, the volume ratio of the reaction solvent toluene to the potassium carbonate aqueous solution is 4:1;

[0048] And / or, the reaction temperature in step 2) is 90°C.

[0049] The present invention also provides the use of the organic semiconductor material containing a sulfone group structure represented by the above formula (I) in the preparation of an organic light emitting transistor OLET, an organic light emitting diode OLED, and an organic field effect transistor OFET.

[0050] According to an embodiment of the present invention, the OLET device uses OTS-modified silicon / silicon dioxide as a substrate and gold as an electrode material.

[0051] The present invention also provides the use of the organic semiconductor material containing a sulfone group structure represented by the above formula (I) in the preparation of an electrode modification layer material.

[0052] Beneficial Effects

[0053] The present invention introduces a sulfone group with strong electron-withdrawing properties into the molecular skeleton, balances the injection and transport characteristics of carriers, and adjusts the energy level of the material to obtain a light-emitting organic semiconductor material with a novel structure as shown in formula (I). The organic semiconductor material shown in formula (I) provided by the present invention has excellent optical properties.

[0054] The light-emitting organic semiconductor material represented by formula (I) provided by the present invention can interact with the electrode material to further regulate the interface energy level, and can be used as an electrode modification layer material.

[0055] The present invention also provides an optical device comprising the light-emitting organic semiconductor material represented by formula (I), such as an OLET device; the optical device provided by the present invention has a simple structure, bipolar transmission characteristics and good electroluminescent characteristics.

[0056] Definition and explanation of terms

[0057] Unless otherwise specified, the definitions of groups and terms recorded in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, definitions of specific compounds in examples, etc., can be arbitrarily combined and combined with each other. The definitions of groups and compound structures after such combinations and combinations should be understood to be within the scope of the specification and / or claims of this application.

[0058] Unless otherwise specified, the numerical ranges recorded in this specification and claims are equivalent to recording at least each specific integer value therein. For example, the numerical range "1-20" is equivalent to recording each integer value in the numerical range "1-20", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer value in the numerical range "11-20", namely 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0059] The term "halogen" or "halo" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0060] In addition, it should be noted that, unless otherwise explicitly stated, the description method "...independently selected" used in the present invention should be understood in a broad sense, meaning that the individuals described are independent of each other and can be independently selected from the same or different specific groups. In more detail, the description method "...independently selected" can mean that in different groups, the specific options expressed by the same symbols do not affect each other; it can also mean that in the same group, the specific options expressed by the same symbols do not affect each other.

[0061] In various parts of this specification, the substituents of the compounds disclosed in the present invention are disclosed according to group types or ranges. It is particularly pointed out that the present invention includes each independent subcombination of the individual members of these group types and ranges. For example, the term "C 1-6 "Alkyl" refers specifically to an independently disclosed C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl or C 6 alkyl.

[0062] In various parts of the present invention, linking substituents are described. When the structure clearly requires a linking group, the Markush variable listed for that group should be understood as a linking group. For example, if the structure requires a linking group and the Markush group definition for that variable lists "alkyl" or "aryl", it should be understood that the "alkyl" or "aryl" represents an alkylene group or an arylene group, respectively, that is linked.

[0063] The term "C1-20 "Alkyl" means a straight or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, "C 1-6 "Alkyl" means straight chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group may be optionally substituted with one or more substituents described herein. In some embodiments, the alkyl group contains 1-12 carbon atoms; in other embodiments, the alkyl group contains 1-6 carbon atoms; in yet other embodiments, the alkyl group contains 1-4 carbon atoms. Examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl butyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl or the like or isomers thereof.

[0064] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0065] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 This is the fluorescence spectrum of the material of Example 2-3.

[0067] Figure 2 The transfer curves and electroluminescence photos of the p-channel and n-channel of the device under source-drain voltage conditions of -40V and 90V.

[0068] Figure 3Device structure and bipolar transfer curve using DNaDBSO-type materials as modification layer. DETAILED DESCRIPTION

[0069] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0070] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0071] Example 1: Synthesis of 3,7-dibromodibenzothiophene sulfone

[0072]

[0073] Under ice bath conditions, 2.15g of dibenzothiophene sulfone was dissolved in 70ml of concentrated sulfuric acid in a 150ml reaction bottle, and N-bromosuccinimide NBS (3.83g) was added in batches. Then the reaction bottle was stirred at room temperature for about half a day. After the reaction was completed, the reaction solution was poured into a large amount of water and filtered. After the filter cake was dried, petroleum ether / dichloromethane was used as the eluent and purified by silica gel column chromatography to obtain a white solid (2.4g, yield 64%). The H NMR spectrum showed that it was the target product 3,7-dibromodibenzothiophene sulfone: 1 HNMR (400MHz, CDCl 3 ): δ7.94(d,2H),7.76-7.79(dd,J=8.2Hz,1.7Hz,2H),7.63(d,J=8.2Hz,2H).

[0074] Example 2: Synthesis of 3,7-dinaphthyldibenzothiophene sulfone (DNaDBSO)

[0075]

[0076] Under argon protection, add 3,7-dibromodibenzothiophene sulfone (500 mg), naphthalene boronic acid (686 mg), tetrakis(triphenylphosphine) palladium catalyst (309 mg), potassium carbonate (1.105 g) prepared in Example 1 to a 50 ml reaction bottle, and then inject 16 ml of degassed toluene and 4 ml of water into the reaction bottle. The reaction was stirred at 90 ° C for 25 hours. After the reaction was completed, the reaction solution was washed with water and extracted with chloroform, and the organic phase was dried with magnesium sulfate and the solvent was dried. The solid was purified by silica gel column chromatography with chloroform as the eluent to obtain a light yellow solid (363 mg, yield 58%). The H NMR spectrum showed that it was the target product 3,7-dinaphthyldibenzothiophene sulfone: 1H NMR (400 MHz, CDCl 3 ): δ8.21(s,2H),8.13(s,2H),7.89-8.03(m,10H),7.77(dd,J=8.2Hz,2H),7.56(m,4H).

[0077] Example 3: Synthesis of 3,7-di(6-tert-butyl-2-naphthyl)dibenzothiophene sulfone (t-Bu-DNaDBSO)

[0078]

[0079] Under argon protection, 3,7-dibromodibenzothiophene sulfone (400 mg), 6-tert-butyl-2-naphthaleneboronic acid pinacol ester (713 mg), and tetrakis(triphenylphosphine)palladium catalyst (198 mg) prepared in Example 1 were added to a 50 ml reaction bottle, and then 25.6 ml of degassed toluene and 6.4 ml of 2M potassium carbonate aqueous solution were injected into the reaction bottle. The reaction was stirred at 90 ° C for 24 hours. After the reaction was completed, the reaction solution was washed with water and extracted with chloroform, and the organic phase was dried with magnesium sulfate and the solvent was dried. The solid was purified by silica gel column chromatography with chloroform as the eluent to obtain a slightly yellow solid (493 mg, yield 79%). The nuclear magnetic hydrogen spectrum showed that it was the target product 3,7-di(6-tert-butyl-2-naphthyl)dibenzothiophene sulfone: 1 H NMR (400 MHz, CDCl 3 ): δ8.20(d,J=1.5Hz,2H),8.08(s,2H),8.01(dd,J=8.0Hz,1.6Hz,2H),7.95-7.87(m,6H), 7.82(s,2H),7.75(dd,J=8.5Hz,1.8Hz,2H),7.67(dd,J=8.7Hz,1.9Hz,2H),1.45(s,18H).

[0080] Example 4: Measurement of optical properties of DNaDBSO-based materials

[0081] The fluorescence spectrum of the material prepared in Example 2-3 was measured using a fluorescence spectrometer. Figure 1 As shown, the position of the fluorescence emission peak of the material in the solid state is 450-461nm, which belongs to a blue light material. The quantum yield of the material prepared in Example 2-3 was measured by using an integrating sphere, and the results showed that the solid state quantum yield of the material exceeded 40%, and it was a good luminescent material.

[0082] Example 5: Measurement of electrical properties of DNaDBSO-based materials

[0083] Micro-nanocrystals of DNaDBSO material were grown on OTS-modified silicon / silicon dioxide substrates, and gold electrodes prepared by masking were attached to the crystals using a probe to construct OFET devices. The transfer curves of the p-channel and n-channel of the device were measured at source-drain voltages of -40V and 90V, respectively. The results are shown in Figure 2. Figure 2 As shown, the device exhibits obvious bipolar transport characteristics and electroluminescent behavior, so the device is also considered to be an OLET device.

[0084] Example 6: Measurement of DNaDBSO-based materials as interface modification layers

[0085] An organic layer (p-type material) is grown on a common OFET substrate, and then a layer of DNaDBSO-type material is evaporated, and finally the electrode material is evaporated to construct the device. By taking appropriate source and drain voltages, the bipolar transport characteristics of the material can be modulated. The results are as follows Figure 3 shown.

[0086] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. Organic semiconductor material containing a sulfone structure represented by formula (I): in, M is a core unit selected from the following sulfone-containing structures: A is independently selected from S, Se; represents the attachment site of the group; R1 and R2 are the same or different and are independently selected from the following aryl or heteroaryl groups: R3 are the same or different and are independently selected from H, halogen, cyano, C 1-20 Alkyl, halogen substituted C 1-20 Alkyl; n is selected from any natural number between 0 and 10.

2. The organic semiconductor material containing a sulfone structure according to claim 1, characterized in that: C 1-20 Alkyl groups include C 1-20 Straight chain alkyl or C 1-20 Branched chain alkyl; and / or, C 1-20 Alkyl is C 1-12 Alkyl, more preferably C 1-6 Alkyl groups, such as tert-butyl; and / or, M is A is selected from S and Se. And / or, R1, R2 are the same or different and are independently selected from the group: and / or, R3 are the same or different and are independently selected from H, C 1-6 alkyl.

3. The organic semiconductor material containing a sulfone structure according to claim 1 or 2, characterized in that: The light-emitting organic semiconductor material containing a sulfone structure represented by formula (I) is represented by formula (II): A is selected from S and Se; R3 are the same or different and are independently selected from H, halogen, cyano, C 1-20 Alkyl, halogen substituted C 1-20 alkyl; n is selected from any natural number between 0 and 10.

4. The organic semiconductor material containing a sulfone structure according to claim 3, characterized in that: R3 is the same; and / or, R3 is selected from H, C 1-12 Alkyl (e.g. C 1-6 alkyl, such as tert-butyl); And / or, n is selected from any natural number between 0-3.

5. A method for preparing an organic semiconductor material containing a sulfone group structure represented by formula (I) according to claim 1 or 2, the method comprising the following steps: 1) a compound containing a core unit of a sulfone structure undergoes a bromine substitution reaction to obtain a bromine substituted product; 2) The bromine-substituted product obtained in step 1) is subjected to a Suzuki coupling reaction with an aryl boronic acid or a heteroaryl boronic acid (or an aryl boronic acid pinacol ester or a heteroaryl boronic acid pinacol ester) to obtain an organic semiconductor material containing a sulfone group structure as shown in formula (I).

6. A method for preparing an organic semiconductor material containing a sulfone group structure represented by formula (II) according to claim 3 or 4, the method comprising the following steps: 1) Compound 1 containing a core unit of a sulfone structure undergoes a bromine substitution reaction to obtain a bromine substituted product 2; The reaction formula is as follows: 2) the bromine-substituted product 2 obtained in step 1) is subjected to a Suzuki coupling reaction with an aryl boronic acid or an aryl boronic acid pinacol ester to obtain an organic semiconductor material containing a sulfone group structure represented by formula (II); The reaction formula is as follows: In the formula, A, R3 and n have the definitions as described in formula (II) according to claim 3 or 4.

7. The preparation method according to claim 5 or 6, characterized in that: In step 1), the bromination reagent is NBS; And / or, in step 1), concentrated sulfuric acid is added to the reaction system; And / or, the reaction temperature in step 1) is room temperature; and / or, step 2) is carried out under an inert gas (e.g., argon) atmosphere; And / or, step 2) the reaction solvent is toluene; And / or, the catalyst for the reaction in step 2) is tetrakistriphenylphosphine palladium; And / or, step 2) adding potassium carbonate to the reaction system; preferably, the concentration of the potassium carbonate solution is 2 mol / L; further preferably, the volume ratio of the reaction solvent toluene to the potassium carbonate aqueous solution is 4:1; And / or, the reaction temperature in step 2) is 90°C.

8. Use of the organic semiconductor material containing a sulfone structure represented by formula (I) according to any one of claims 1 to 4 in the preparation of an organic light emitting transistor OLET, an organic light emitting diode OLED, and an organic field effect transistor OFET; Preferably, the OLET device uses OTS-modified silicon / silicon dioxide as a substrate and gold as an electrode material.

9. Use of the organic semiconductor material containing a sulfone structure represented by formula (I) according to any one of claims 1 to 4 in the preparation of electrode modification layer materials.

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