Cyanated butadiene derivatives, methods for their preparation and use, and polymer semiconductor materials, methods for their preparation and use

Abstract

This invention relates to the fields of organic synthesis and organic electronics, particularly to cyanobutadiene derivatives and their preparation methods and applications, and polymer semiconductor materials and their preparation methods and applications. The cyanobutadiene derivatives have the following general structural formula (1) or (2): This invention develops a series of cyanobutadiene derivative-based electron-deficient building blocks with simple structures, strong electron-withdrawing capabilities, and easy synthesis. These electron-deficient building blocks can be used as acceptor units in the development of organic photovoltaic, organic thermoelectric, and organic field-effect transistor materials.

Description

Technical Field

[0001] This invention relates to the fields of organic synthesis and organic electronics, and particularly to cyanobutadiene derivatives and their preparation methods and applications, as well as polymer semiconductor materials and their preparation methods and applications. Background Technology

[0002] Polymer semiconductor materials possess advantages such as light weight, flexibility, and solution-processability, giving them unique strengths in fabricating large-area, fully flexible, and low-cost devices. After decades of research, the performance of organic field-effect transistors (OFETs) has made significant progress. However, compared to P-type polymer semiconductor materials (hole transport type), the development of N-type polymer semiconductor materials (electron transport type) is relatively lagging, which restricts the commercial application of OFETs.

[0003] In the development of N-type polymer semiconductor materials, acceptor structural units play a crucial role. The introduction of electron-deficient groups during the construction of acceptor structural units leads to reduced reactivity, increasing the difficulty and cost of their synthesis. Therefore, developing acceptor structural units with simple structures and easy synthesis is of great significance for promoting the development of N-type polymer semiconductor materials.

[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0005] The present invention aims to overcome the problems of complex electron-deficient unit structure, limited variety, and difficult synthesis of N-type polymers in the development of existing technologies. Therefore, it provides a cyanobutadiene derivative and its preparation method and application, as well as a polymer semiconductor material and its preparation method and application, to overcome the above-mentioned shortcomings.

[0006] To achieve the above-mentioned objectives, the present invention is implemented through the following technical solution:

[0007] In a first aspect, the present invention provides a cyanobutadiene derivative, the general structural formula of which is shown in formula (1) or formula (2) below:

[0008]

[0009] in:

[0010] In formula (1), X and Y are independently selected from any one of H, F, Cl, Br, I, CN, NO2, NR1R2, wherein R1 and R2 are independently selected from any one of H, C2-C99 alkyl, alkenyl, alkynyl, and amide groups; M and N are independently selected from any one of F, Cl, Br, I, and sulfonate groups; when X and Y are H, M and N are not simultaneously bromine.

[0011] In formula (2), Ar1 is selected from any one of substituted or unsubstituted thiophene, substituted or unsubstituted thiazole, substituted or unsubstituted thiadiazole, substituted or unsubstituted furan, substituted or unsubstituted selenophene, substituted or unsubstituted imide, substituted or unsubstituted benzene ring, substituted or unsubstituted pyridine, substituted or unsubstituted pyridazine, and substituted or unsubstituted pyrazine; the substituents on Ar1 are selected from any one of C2-C99 straight chain, branched chain, ether chain, silyl chain, C3-C99 chain alkyl chain containing polycyclic rings, F, Cl, Br, I, CN, NO2, and NR3R4, wherein R3 and R4 are independently selected from any one of H, C2-C99 alkyl, alkenyl, alkynyl, and amide groups; and P and Q are independently selected from any one of F, Cl, Br, I, and sulfonate groups.

[0012] Preferably, the cyanobutadiene derivative is selected from any one of the following formulas TM1-TM39;

[0013]

[0014]

[0015] Secondly, the present invention also provides a method for preparing the cyanobutadiene derivative as described above, comprising at least the following steps:

[0016] A benzene ring derivative containing an ortho-diamine structure was reacted with lead tetraacetate to obtain a cyanobutadiene derivative.

[0017] Preferably, the benzene ring derivative containing the ortho-diamine structure can be halogenated before reacting with lead tetraacetate to obtain the cyanobutadiene derivative. A typical reaction pathway can be seen in the following steps:

[0018] Step 1. Add raw material 4 and liquid bromine to acetic acid solution and leave at room temperature overnight to obtain intermediate 5;

[0019] Step 2. Add intermediate 5 and lead tetraacetate to a toluene solution and heat at 50-80°C overnight to obtain the cyanobutadiene derivative TM2. The reaction pathway is shown in the following formula:

[0020]

[0021] Preferably, the benzene ring derivative containing the ortho-diamine structure can be halogenated before reacting with lead tetraacetate to obtain the cyanobutadiene derivative. A typical reaction pathway can be seen in the following steps:

[0022] Step 1. Add raw material 7 and liquid bromine to acetic acid solution and leave at room temperature overnight to obtain intermediate 8;

[0023] Step 2. Add intermediate 8 and lead tetraacetate to a toluene solution and heat at 50-80°C overnight to obtain the cyanobutadiene derivative TM8. The reaction pathway is shown in the following diagram:

[0024]

[0025] Preferably, the benzene ring derivative containing the ortho-diamine structure can be halogenated before reacting with lead tetraacetate to obtain the cyanobutadiene derivative. A typical reaction pathway can be found in the following steps:

[0026] Step 1. Add raw material 10 and liquid bromine to acetic acid solution and leave at room temperature overnight to obtain intermediate 11;

[0027] Step 2. Add intermediate 11 and lead tetraacetate to a toluene solution and heat at 50-80°C overnight to obtain the cyanobutadiene derivative TM20. The reaction pathway is shown in the following formula:

[0028]

[0029] Preferably, the preparation method further includes the step of reducing a benzene ring derivative containing a thiadiazole or ortho-dinitro structure to obtain a benzene ring derivative containing an ortho-diamine structure.

[0030] Preferably, the reduction method of the benzene ring derivative containing the thiadiazole structure is as follows: reacting the benzene ring derivative containing the thiadiazole structure with sodium borohydride to obtain a benzene ring derivative having an ortho-diamine structure.

[0031] Preferably, the method for preparing the final cyanobutadiene derivative from a benzene ring derivative containing a thiadiazole structure includes:

[0032] (1) Reduce the benzene ring derivative containing the thiadiazole structure to obtain the benzene ring derivative with the ortho-diamine structure;

[0033] (2) The benzene ring derivative with the ortho-diamine structure was reacted with lead tetraacetate to obtain the cyanobutadiene derivative.

[0034] Further preferred methods for preparing cyanobutadiene derivatives from benzene ring derivatives containing a thiadiazole structure can refer to the following technical solutions:

[0035] Step 1. Add raw material 1 and sodium borohydride to ethanol, stir and react overnight at room temperature to obtain intermediate 2;

[0036] Step 2. Add intermediate 2 and lead tetraacetate to a toluene solution and heat at 50-80°C overnight to obtain the cyanobutadiene derivative TM1. The reaction pathway of this scheme is shown below:

[0037]

[0038] Further preferred methods for preparing cyanobutadiene derivatives from benzene ring derivatives containing a thiadiazole structure may also refer to the following technical solutions:

[0039] Step 1. Add raw material 13 and sodium borohydride to ethanol, stir and react overnight at room temperature to obtain intermediate 14;

[0040] Step 2. Add intermediate 14 and lead tetraacetate to a toluene solution and heat at 50-80°C overnight to obtain the cyanobutadiene derivative TM29. The reaction pathway of this scheme is shown below:

[0041]

[0042] Further preferred methods for preparing cyanobutadiene derivatives from benzene ring derivatives containing a thiadiazole structure may also refer to the following technical solutions:

[0043] Step 1. Add raw material 16 and zinc powder to acetic acid, stir and react overnight at room temperature to obtain intermediate 17;

[0044] Step 2. Add intermediate 17 and lead tetraacetate to a toluene solution and heat at 50-80°C overnight to obtain the cyanobutadiene derivative TM31. The reaction pathway of this scheme is shown below:

[0045]

[0046] Preferably, the reduction method of the benzene ring derivative containing the ortho-dinitro structure is as follows: react the benzene ring derivative containing the ortho-dinitro structure with zinc powder to obtain a benzene ring derivative with the ortho-diamine structure.

[0047] Further preferred methods for preparing cyanobutadiene derivatives from benzene ring derivatives containing ortho-dinitro structures may also refer to the following technical solutions:

[0048] Step 1. Add raw material 19 and zinc powder to acetic acid, stir and react overnight at room temperature to obtain intermediate 20;

[0049] Step 2. Add intermediate 20 and lead tetraacetate to a toluene solution and heat at 50-80°C overnight to obtain the cyanobutadiene derivative TM35. The reaction pathway of this scheme is shown below:

[0050]

[0051] Thirdly, the present invention also provides a polymer semiconductor material whose structure is based on the cyanobutadiene derivatives described above, and the general formula of the polymer semiconductor material is shown in formula (3) or formula (4) below:

[0052]

[0053] In formula (3), n is an integer from 8 to 500; Ar2 is selected from any one of substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted vinyl, substituted or unsubstituted ethynyl, substituted or unsubstituted pyrrolopyrroledione unit, or substituted or unsubstituted benzene ring; the substituents on Ar2 are selected from any one of C2-C99 straight chain, branched chain, ether chain, silane chain, C3-C99 alkyl chain containing polycyclic rings, F, Cl, Br, I, CN, NO2, NR5R6, wherein R5 and R6 are independently selected from any one of H, C2-C99 alkyl, alkenyl, ethynyl, or amide group;

[0054] In formula (4), n is an integer from 8 to 500; Ar3 is selected from any one of substituted or unsubstituted thiophene, substituted or unsubstituted selenophene, substituted or unsubstituted vinyl, substituted or unsubstituted ethynyl, substituted or unsubstituted pyrrolopyrroledione unit, or substituted or unsubstituted benzene ring; the substituents on Ar3 are selected from C2-C99 straight chain, branched chain, ether chain, silane chain, C3-C99 alkyl chain containing polycyclic rings, F, Cl, Br, I, CN, NO2, NR7R8, wherein R7 and R8 are independently selected from any one of H, C2-C99 alkyl, alkenyl, ethynyl, or amide group.

[0055] Preferably, the polymer semiconductor material is selected from any one of the following formulas P1-P25:

[0056]

[0057]

[0058] Fourthly, the present invention also provides a method for preparing a polymer semiconductor material as described above, comprising at least the following steps:

[0059] The polymer semiconductor material shown in formula (3) is synthesized by reacting the copolymer unit Ar2 with the copolymer unit Ar2 via a Stille coupling reaction; or, the polymer semiconductor material shown in formula (4) is synthesized by reacting the copolymer unit Ar3 with the copolymer unit Ar2 via a Stille coupling reaction.

[0060] The reaction formula is shown below:

[0061]

[0062] Fifthly, the present invention also provides the application of the cyanobutadiene derivative or the polymer semiconductor material in N-type polymer semiconductors.

[0063] Preferably, the N-type polymer semiconductor is applied to any one of organic field-effect transistors, organic thermoelectric devices, organic solar cells, and organic light-emitting diodes.

[0064] The present invention has the following beneficial effects:

[0065] The cyano functional group possesses strong electron-withdrawing properties and is widely used in the development of N-type organic semiconductor materials. Cyanothiophene derivatives are a classic structural unit. However, the electron-rich nature of thiophene results in insufficient electron-deficient properties, limiting its application. This invention introduces the cyano functional group into electrically neutral or weakly electron-deficient butadiene derivatives, developing a series of simple, electron-withdrawing, and easily synthesized cyanobutadiene-based electron-deficient building blocks. These electron-deficient building blocks can serve as acceptor units in the development of organic photovoltaics, organic thermoelectrics, and organic field-effect transistor materials. In organic field-effect transistor devices, to achieve N-type performance, the LUMO level of the material typically needs to reach around -4.0 eV. Cyclic voltammetry testing shows that the electrochemical energy level (LUMO level) of the polymer semiconductor material in this invention can reach -4.02 eV, indicating its potential application as an excellent N-type semiconductor polymer, further demonstrating the significant advantages of cyanobutadiene derivatives in N-type polymer semiconductor applications.

[0066] In summary, this invention provides a series of simple, easy-to-synthesize, and electron-withdrawing electron-deficient building blocks, which not only enriches the types of acceptor units but also lays the foundation for the future industrialization of organic electronics and promotes the development of organic semiconductor materials. Attached Figure Description

[0067] Figure 1 For TM2 1 H-NMR spectrum (deuterated chloroform).

[0068] Figure 2 For TM8 1 H-NMR spectrum (deuterated chloroform).

[0069] Figure 3 For TM20 13 C-NMR spectrum (deuterated chloroform).

[0070] Figure 4 The electrochemical test curve for P10 is shown.

[0071] Figure 5 This is a schematic diagram of the specific structure of the field-effect transistor device in Example 13.

[0072] Figure 6 The graph shows the test results of the charge transport properties of the P10 polymer.

[0073] in: Figure 6 (a) is the transfer curve of the device, and (b) is the output curve of the device. Detailed Implementation

[0074] The present invention will be further described below with reference to specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below are generally only some, not all, of the embodiments of the present invention. Therefore, all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0075] Example 1: Preparation of TM1

[0076]

[0077] Add raw material 1 (10 g, 34.36 mmol) and sodium borohydride (1.9 g, 51.54 mmol) to 250 mL of ethanol and stir overnight at room temperature to obtain intermediate 2. Add intermediate 2 and lead tetraacetate to toluene solution and heat at 60 °C overnight to obtain cyanobutadiene derivative TM1 (4.7 g, 53%). 1 H NMR (400MHz, CDCl3): δppm 7.44 (s, 2H). 13 C NMR (100MHz, CDCl3).

[0078] Example 2: Preparation of TM2

[0079]

[0080] Raw material 4 (10 g, 79.36 mmol) and 10 mL of liquid bromine in acetic acid were stirred overnight, filtered, washed, and dried to obtain intermediate 5. Intermediate 5 and lead tetraacetate (44.3 g, 100 mmol) were added to toluene solution and reacted at 60 °C overnight. After cooling, the mixture was filtered and column chromatography was performed to obtain product TM2 (10.9 g, 50%). The prepared TM2... 1 H-NMR spectrum (deuterated chloroform) as shown Figure 1 As shown, 1H NMR (400MHz, CDCl3): δppm 7.40 (d, J=23.0Hz, 2H).

[0081] Example 3: Preparation of TM8

[0082]

[0083] Raw material 7 (10 g, 69.44 mmol) and 10 mL of liquid bromine in acetic acid solution were stirred overnight, filtered, washed, and dried to obtain intermediate 8. Intermediate 8 and lead tetraacetate (44.3 g, 100 mmol) were then added to toluene solution and reacted overnight at 60 °C. After cooling, the mixture was filtered and column chromatography was performed to obtain product TM18 (9.4 g, 46%). The prepared TM8... 19 F-NMR spectrum (deuterated chloroform) as shown Figure 2 As shown, 19 F NMR (377MHz, CDCl3): δppm-91.74.

[0084] Example 4: Preparation of TM20

[0085]

[0086] Starting material 10 (10 g, 63.29 mmol) and 10 mL of liquid bromine in acetic acid were stirred overnight, filtered, washed, and dried to obtain intermediate 11. Intermediate 11 and lead tetraacetate (44.3 g, 100 mmol) were then added to toluene solution and reacted overnight at 60 °C. After cooling, the mixture was filtered and column chromatography was performed to obtain product TM20 (7.4 g, 38%). TM20... 13 C-NMR spectrum (deuterated chloroform) as shown Figure 3 As shown, 13 C NMR (100MHz, CDCl3): δppm 121.28, 112.52, 111.53, 110.79.

[0087] Example 5: Preparation of TM29

[0088]

[0089] Add raw material 13 (5 g, 13.85 mmol) and sodium borohydride (0.78 g, 20.77 mmol) to 200 mL of ethanol and stir overnight at room temperature to obtain intermediate 14. Add intermediate 14 and lead tetraacetate to toluene solution and heat at 60 °C overnight to obtain cyanobutadiene derivative TM29 (3.1 g, 46%).

[0090] Example 6: Preparation of TM31

[0091] Raw material 16 and zinc powder were added to acetic acid and stirred overnight at room temperature to obtain intermediate 17. Intermediate 17 and lead tetraacetate were added to toluene solution and heated overnight at 60°C to obtain cyanobutadiene derivative TM31.

[0092] Example 7: Preparation of TM35

[0093] Add raw material 19 and zinc powder to acetic acid and stir overnight at room temperature to obtain intermediate 20. Add intermediate 20 and lead tetraacetate to toluene solution and heat at 50-80℃ overnight to obtain cyanobutadiene derivative TM35.

[0094] Example 8: Preparation of P10

[0095]

[0096] TM8 (29.5 mg, 0.1 mmol), 2,5-bis(2-octyldodecyl)-3,6-bis(5-(trimethylstanyl)thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrolo-1,4-dione (118.8 mg, 0.1 mmol), Pd2(dba)3 (1.37 mg), and P(o-tol)3 (3.65 mg) were dissolved in freshly distilled toluene. The mixture was reacted under nitrogen protection at 140 °C for 3 h using a microwave oven. After the reaction was complete, the reaction solution was precipitated by adding methanol dropwise. The resulting solid was extracted with petroleum ether, acetone, and n-hexane. The remaining fraction was eluted with chloroform and collected to obtain P10. The GPC polymer parameters were (M... n =55.6kDa, PDI=2.7).

[0097] Example 9: Preparation of P7

[0098]

[0099] TM8 (29.5 mg, 0.1 mmol), 5,5'-bis(trimethyltinyl)-[2,2'-bithiophene]-3,3'-dicarboxynitrile (53.4 mg, 0.1 mmol), Pd2(dba)3 (1.37 mg), and P(o-tol)3 (3.65 mg) were dissolved in freshly distilled toluene. The mixture was reacted under nitrogen protection and microwaved at 140 °C for 3 h. After the reaction was completed, the reaction solution was precipitated by adding methanol dropwise. The resulting solid was extracted with petroleum ether, acetone, and n-hexane. The remaining fraction was eluted with chloroform and collected to give P7.

[0100] Example 10: Preparation of P15

[0101]

[0102] TM29 (29.5 mg, 0.1 mmol), 2,5-bis(trimethyltinyl)selenophene (45.6 mg, 0.1 mmol), Pd2(dba)3 (1.37 mg), and P(o-tol)3 (3.65 mg) were dissolved in freshly distilled toluene. The mixture was reacted under nitrogen protection and microwaved at 140 °C for 3 h. After the reaction was completed, the reaction solution was precipitated by adding methanol dropwise. The resulting solid was extracted with petroleum ether, acetone, and n-hexane. The remaining fraction was eluted with chloroform and collected to give P15.

[0103] Example 11: Preparation of P19

[0104]

[0105] TM29 (29.5 mg, 0.1 mmol), 5,5'-bis(trimethyltinyl)-[2,2'-bithiophene]-3,3'-dicarboxynitrile (53.4 mg, 0.1 mmol), Pd2(dba)3 (1.37 mg), and P(o-tol)3 (3.65 mg) were dissolved in freshly distilled toluene. The mixture was reacted under nitrogen protection and microwaved at 140 °C for 3 h. After the reaction was completed, the reaction solution was precipitated by adding methanol dropwise. The resulting solid was extracted with petroleum ether, acetone, and n-hexane. The remaining fraction was eluted with chloroform and collected to obtain P19.

[0106] Example 12: Study on the electrochemical properties of P10

[0107] The electrochemical energy levels of polymer P10 were tested using cyclic voltammetry. The electrochemical test curves for P10 are shown below. Figure 4 As shown in the figure. The test results show that the LUMO energy level of P10 can reach -4.02 eV, indicating that P10 is an excellent N-type semiconductor polymer, further demonstrating that cyanobutadiene derivatives have significant advantages in N-type polymer semiconductor applications.

[0108] Example 13: Application of P10 in organic field-effect transistors

[0109] In this embodiment, the charge transport performance of the P10 polymer was tested by fabricating an organic field-effect transistor device, using a top-gate top-contact device structure. The specific structure of the device is as follows: Figure 5 As shown.

[0110] like Figure 6 The transfer curve (a) and output curve (b) of the device are shown below. The channel length and channel width of the organic field-effect transistor are 50 μm and 5 mm, respectively. Test results show that after thermal annealing under optimal conditions, the polymer exhibits good unipolar N-type performance. The saturated electron mobility of the device reaches 1.02 cm⁻¹. 2 V -1 s-1 With a threshold voltage of 21V, it can achieve 10 3 The switching ratio.

[0111] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A cyanobutadiene derivative, characterized in that, The cyanobutadiene derivative is selected from any one of the following formulas TM1-TM28: 。 2. A method for preparing the cyanobutadiene derivative as described in claim 1, characterized in that, At least the following steps are included: A benzene ring derivative containing an ortho-diamine structure was reacted with lead tetraacetate to obtain a cyanobutadiene derivative.

3. The method for preparing the cyanobutadiene derivative according to claim 2, characterized in that, It also includes the step of reducing a benzene ring derivative containing an ortho-dinitro structure to obtain a benzene ring derivative containing an ortho-diamine structure.

4. The method for preparing the cyanobutadiene derivative according to claim 3, characterized in that, The reduction method for the benzene ring derivative containing the ortho-dinitro structure is as follows: A benzene ring derivative containing an ortho-dinitro group is reacted with zinc powder to obtain a benzene ring derivative with an ortho-diamine group.

5. A polymer semiconductor material based on the cyanobutadiene derivative as described in claim 1, characterized in that, The polymer semiconductor material is selected from any one of the following formulas: P1-P11 and P25. Where n is an integer between 8 and 500.

6. A method for preparing a polymer semiconductor material as described in claim 5, characterized in that, At least the following steps are included: The polymer semiconductor material shown in formula (3) is synthesized by coupling formula (1) with the copolymer unit Ar2 via a Stille coupling reaction; wherein, formula (1) is the cyanobutadiene derivative of claim 1; The reaction formula is shown below: 。 7. The application of the cyanobutadiene derivative as described in claim 1 or the polymer semiconductor material as described in claim 5 in N-type polymer semiconductors.

8. The application according to claim 7, characterized in that, The N-type polymer semiconductor is applied to any one of organic field-effect transistors, organic thermoelectric devices, organic solar cells, and organic light-emitting diodes.

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