A tetracyanoanthracene derivative with double end substitution structure, and a preparation method and application thereof

Abstract

The application discloses a tetracyanoanthracene derivative with a double-end substitution structure and a preparation method and application thereof, and a structural general formula of the tetracyanoanthracene derivative is as follows: wherein R is selected from -F, -NO2, -CN or C n H 2n+1 (n is an integer between 0 and 20) one of them. The application introduces an aromatic ethylene bridging unit with conjugate expansion capacity on both sides of the tetracyanoanthracene core structure, and introduces a substitution group with adjustable structure at the end of the aromatic ring, which not only enhances the conjugation and pi-pi stacking ability of the molecule, is conducive to the ordered transmission of carriers in the solid-state thin film, but also helps to improve the crystallinity, surface flatness and air stability of the thin film, and improves the overall performance and environmental adaptability of the device. The tetracyanoanthracene derivative material with the double-end substitution structure provided in the application exhibits higher electron mobility, lower opening voltage and more excellent air operation stability in the OFET device.

Description

Technical Field

[0001] This invention relates to the field of n-type organic semiconductor materials technology, and more specifically, to a tetracyananthracene derivative having a dual-terminal substituted structure, its preparation method, and its application. Background Technology

[0002] Organic field-effect transistors (OFETs) have attracted widespread attention in recent years as core components for next-generation flexible electronics, wearable devices, logic circuits, and organic optoelectronic integrated systems due to their advantages such as low cost, mechanical flexibility, and solution processability.

[0003] As device performance requirements increase, research on organic semiconductor materials for OFETs has gradually expanded from p-type (hole transport) materials to n-type (electron transport) materials. In particular, the demand for high-mobility and air-stable n-type organic semiconductor materials is becoming increasingly urgent in large-area integration and CMOS circuit applications.

[0004] Among known n-type organic semiconductor materials, molecular systems with rigid conjugated frameworks such as perylene, tetrabenzo[b,d,f,h]thiophene (TBT), and anthracene as the core, modified by introducing electron acceptor groups (such as -CN, -F, -COOR), have been extensively studied. In particular, tetracyanoanthracene (TCA) compounds have become important candidates for constructing n-type organic semiconductor materials due to their excellent electron affinity and π-conjugation.

[0005] However, these molecular systems still face several key bottlenecks in device applications:

[0006] (1) Limited energy level control space: Most traditional TCA molecules have symmetrical structures and their LUMO energy level is inherently low. Although this is conducive to electron injection, there is often a lack of means to further control them, making it difficult to meet the energy level matching requirements of different metal electrodes and dielectric layer interfaces.

[0007] (2) Poor film-forming properties and uncontrollable crystallinity: Due to the aggregation effect driven by strong π-π stacking between molecules, the material is prone to forming large-sized grains or non-uniform films during solution processing, which in turn limits the consistency of device performance.

[0008] (3) Insufficient environmental stability: Some TCA materials are prone to decomposition or electronic doping under air or humidity conditions, which leads to rapid degradation of OFET device performance.

[0009] (4) Lack of tunable terminal group modification: Most current TCA derivatives are non-terminal modified or simply substituted aromatic rings, lacking systematic research on the regulation of the relationship between substituent electronic effects, steric hindrance effects and material properties.

[0010] Therefore, there is an urgent need to design and develop novel TCA derivatives with tunable end structures to achieve synergistic optimization of multiple properties such as tunable energy levels, solution processability, thin film uniformity, and device stability while maintaining good electron transport capabilities. Summary of the Invention

[0011] In view of this, the present invention provides a tetracyananthracene derivative with a dual-terminal substituted structure, its preparation method and application.

[0012] Specifically, by introducing conjugated aromatic vinyl bridging units and long-chain alkyl modification groups, this invention achieves synergistic optimization of energy level regulation, molecular stacking regulation, and thin film morphology regulation at the molecular scale, significantly improving the overall performance of the material in OFET devices and overcoming the shortcomings of existing technologies in terms of mobility, film formation, and environmental stability.

[0013] To achieve the above objectives, the technical solution of the present invention is as follows:

[0014] This invention provides a tetracyananthracene derivative with a double-terminal substituted structure, the general structural formula of which is as follows:

[0015]

[0016] R is selected from -F, -NO2, -CN, or C. n H 2n+1 (n is an integer between 0 and 20)

[0017] Specifically, in the structure of the above-mentioned tetracyananthracene derivative with dual-terminal substitution, the central core adopts tetracyananthracene as a strong electron acceptor, providing a lower LUMO energy level to facilitate electron injection; its bridging unit adopts a vinyl structure, providing π-conjugated extension, which helps to regulate molecular energy level and delocalize carriers; its terminal substituent R regulates molecular stacking mode, surface energy, film crystallinity and interface stability by introducing substituents of different sizes and polarities.

[0018] In the above technical solution, the tetracyananthracene derivative with a dual-terminal substituted structure is any one of the following compounds:

[0019]

[0020] The tetracyananthracene derivative with a dual-terminal substituted structure was prepared by the following method:

[0021]

[0022]

[0023] In the above technical solution, the preparation method of the tetracyananthracene derivative with a dual-terminal substituted structure includes the following steps:

[0024] S1. Weigh 2,6-dibromoanthraquinone (A) and malononitrile (B) in proportion, add them to an alcohol solvent, stir until completely dissolved under a nitrogen atmosphere, heat under reflux in the presence of an alkaline catalyst, and after cooling to room temperature, a yellow precipitate is formed to obtain 2,6-dibromotetracyanoanthracene compound (C).

[0025] S2. Dissolve 2,6-dibromotetracyanoanthracene compound (C) in an organic solvent, and slowly and uniformly add a DMF / POCl3 mixture while stirring under ice-water bath conditions. After the addition is complete, stir at room temperature to allow the Vilsmeier reaction to occur, and obtain an aldehyde-containing intermediate (D).

[0026] S3. The aldehyde-containing intermediate (D) obtained in step S2 is condensed with an aryl acetonitrile compound (E) with the desired terminal substitution structure under alkaline catalyst catalysis to introduce conjugated vinyl bridging units at both ends of the molecule, thereby obtaining a tetracyananthracene derivative (T) with a double-terminal substitution structure.

[0027] Specifically, in the above technical solution, in step S2, the organic solvent is dry tetrahydrofuran.

[0028] Preferably, in the above technical solution, in step S2, the amount of dried tetrahydrofuran used is 1000 mL, corresponding to 0.1 mol of 2,6-dibromotetracyanoanthracene compound.

[0029] Specifically, in the above technical solution, in step S2, the volume ratio of DMF to POCl3 in the DMF / POCl3 mixture is 1:1.

[0030] Preferably, in the above technical solution, in step S2, the amount of DMF / POCl3 mixture added is 100 mL, corresponding to 0.1 mol of 2,6-dibromotetracyanoanthracene compound.

[0031] Specifically, in the above technical solution, in step S2, the addition rate of the DMF / POCl3 mixture is controlled by a dropping time of 30-40 minutes.

[0032] Specifically, in the above technical solution, in step S2, the reaction time of the Vilsmeier reaction is 4-6 hours.

[0033] In one specific embodiment of the present invention, step S2 further includes post-processing the aldehyde-containing intermediate obtained from the Vilsmeier reaction.

[0034] Specifically, in the above technical solution, in step S2, the post-processing is as follows: after the Vilsmeier reaction is completed, the mixture is concentrated under reduced pressure, the residue is quenched with ice water and extracted with ethyl acetate, the organic phases are combined, dried with anhydrous sodium sulfate, concentrated by rotary evaporation, and then purified by silica gel column chromatography.

[0035] Preferably, in the above technical solution, in step S2, the eluent for the silica gel column chromatography is petroleum ether / ethyl acetate with a volume ratio of 5:1.

[0036] Specifically, in the above technical solution, in step S3, the condensation reaction is a Wittig-Horner or Knoevenagel condensation reaction, and the reaction time is 8-12 hours.

[0037] Specifically, in the above technical solution, in step S3, the alkaline catalyst is any one of piperidine, ammonium acetate, and sodium hydroxide.

[0038] In one specific embodiment of the present invention, step S3 further includes purifying the product of the condensation reaction. Specifically, after the condensation reaction is completed, the product is cooled to room temperature, the precipitated reddish-brown precipitate is collected, washed 2-3 times with anhydrous ethanol and dried, and finally purified by silica gel column chromatography with dichloromethane / petroleum ether as the eluent in a volume ratio of 2:1 to obtain the final product.

[0039] Specifically, in the above technical solution, in step S1, the alcohol solvent is at least one of anhydrous ethanol, methanol, isopropanol and ethylene glycol.

[0040] Specifically, in the above technical solution, in step S1, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium hydride.

[0041] Specifically, in the above technical solution, in step S1, the reaction time of the heating reflux reaction is 8-15 hours.

[0042] In one specific embodiment of the present invention, step S1 further includes recrystallizing and purifying the precipitated yellow precipitate using ethyl acetate / petroleum ether at a volume ratio of 1:2.5-4 as a recrystallization solvent.

[0043] In another aspect, the present invention provides the application of the above-mentioned tetracyanane anthracene derivative with a double-terminal substituted structure and the tetracyanane anthracene derivative with a double-terminal substituted structure prepared by the above-mentioned preparation method in organic field-effect transistors.

[0044] Compared with the prior art, the present invention has the following advantages:

[0045] This invention introduces aromatic ethylene bridging units with conjugated extension capabilities on both sides of the tetracyananthracene core structure, and introduces tunable substituent groups (alkyl, alkoxy, and other branched structures) at the ends of the aromatic rings. On the one hand, this enhances the conjugation and π-π stacking ability of the molecules, which is beneficial for the orderly transport of charge carriers in solid films. On the other hand, the steric hindrance and hydrophobicity control of the terminal groups help improve the crystallinity, surface smoothness, and air stability of the film, thereby improving the overall performance and environmental adaptability of the device.

[0046] The molecular design strategy proposed in this invention has a clear structure (performance correlation logic) that can achieve synergistic optimization of energy level regulation, thin film quality control and device stability improvement. Compared with the prior art, the tetracyananthracene derivative material with double-terminal substitution structure provided by this invention exhibits higher electron mobility, lower turn-on voltage and better air operation stability in OFET devices, and has good application prospects and promotion value. Detailed Implementation

[0047] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments.

[0048] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Unless otherwise specified, the means used in the embodiments are conventional in the art. The terms "comprising," "including," or any other variations thereof as used herein are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.

[0049] Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0050] Example 1: Preparation of aldehyde-containing intermediates

[0051] The preparation method is as follows:

[0052]

[0053] The specific steps are as follows:

[0054] S1. Weigh 33.6 g (0.10 mol) of 2,6-dibromoanthraquinone (1) and 13.2 g (0.20 mol) of malononitrile (2) and add them to 500 mL of anhydrous ethanol. Stir under nitrogen protection to dissolve them completely. Then add 10 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (8-12 h). After the reaction is completed, cool to room temperature and a large amount of yellow precipitate will precipitate. Filter and collect the filter cake. Wash with anhydrous ethanol to remove residual inorganic salts and by-products. Recrystallize the crude product obtained with ethyl acetate / petroleum ether at a volume ratio of 1:3 as a recrystallization solvent to obtain a yellow needle-like crystalline solid (3).

[0055] S2. Weigh 23.1g (0.05mol) of yellow needle-like crystalline solid (3) and dissolve it in 500mL of dry tetrahydrofuran (THF). Place it in an ice-water bath to cool to 0-5℃. Under stirring, slowly add 50mL of DMF / POCl3 mixture (volume ratio 1:1) (control the addition time to 30-40min). After the addition is complete, remove the ice bath and continue stirring at room temperature until the raw material is completely gone (about 4-6h, TLC monitoring). After the reaction is complete, concentrate under reduced pressure. Quench the residue with ice water and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, concentrate by rotary evaporation, and purify by silica gel column chromatography (eluent: petroleum ether / ethyl acetate volume ratio 5:1) to obtain an orange-yellow solid, which is the intermediate containing aldehyde group (4).

[0056] In step S1, the yield of the yellow needle-like crystalline solid (3) was approximately 78%; its structural analysis results were as follows: 1 H NMR (500MHz, Chloroform) δ7.55-7.36 (m, 4H), 7.10 (d, J=7.5Hz, 2H).

[0057] In step S2, the yield of the aldehyde-containing intermediate (4) was approximately 70%; its structural analysis results were as follows: 1 H NMR (500MHz, Chloroform) δ9.89 (s, 2H), 7.60 (dd, J=7.5, 1.4Hz, 2H), 7.40 (d, J=7.5Hz, 2H), 7.13 (d, J=1.4Hz, 2H).

[0058] Example 2: Synthesis of representative compound T-1

[0059] The synthesis method is as follows:

[0060]

[0061] The specific steps are as follows:

[0062] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 2.4 g (20 mmol) of phenylacetonitrile (T-1-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-1).

[0063] The yield of compound T-1 was approximately 65%; its structural analysis results were as follows: 1 H NMR (500MHz, Chloroform) δ7.82-7.65 (m, 6H), 7.55-7.36 (m, 6H), 7.21 (d, J=1.4Hz, 4H), 6.74 (t, J=1.4Hz, 2H).

[0064] Example 3: Synthesis of representative compound T-2

[0065] The synthesis method is as follows:

[0066]

[0067] The specific steps are as follows:

[0068] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 2.6 g (20 mmol) of 4-methylphenylacetonitrile (T-2-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-2).

[0069] The yield of compound T-2 was approximately 64%; its structural analysis results are as follows: 1 H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.46-7.25 (m, 4H), 7.24-6.96 (m, 8H), 6.74 (t, J = 1.4Hz, 2H), 2.41 (s, 6H).

[0070] Example 4: Synthesis of representative compound T-3

[0071] The synthesis method is as follows:

[0072]

[0073] The specific steps are as follows:

[0074] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 2.9 g (20 mmol) of 4-ethylphenylacetonitrile (T-3-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-3).

[0075] The yield of compound T-3 was approximately 73%; its structural analysis results are as follows: 1 H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.47-7.28 (m, 4H), 7.21 (d, J=1.4Hz, 4H), 6.91-6.48 (m, 6H), 2.72 (q, J=13.2Hz, 4H), 1.18 (t, J=13.2Hz, 6H).

[0076] Example 5: Synthesis of representative compound T-4

[0077] The synthesis method is as follows:

[0078]

[0079] The specific steps are as follows:

[0080] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 3.2 g (20 mmol) of 4-propylphenylacetonitrile (T-4-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-4).

[0081] The yield of compound T-4 was approximately 81%; its structural analysis results are as follows: 1H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.49-7.28 (m, 4H), 7.21 (d, J=1.4Hz, 4H) , 6.94-6.52 (m, 6H), 2.76-2.30 (m, 4H), 1.79-1.38 (m, 4H), 0.94 (t, J=13.2Hz, 6H).

[0082] Example 6: Synthesis of representative compound T-5

[0083] The synthesis method is as follows:

[0084]

[0085] The specific steps are as follows:

[0086] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 3.8 g (20 mmol) of 4-pentylphenylacetonitrile (T-5-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-5).

[0087] The yield of compound T-5 was approximately 84%; its structural analysis results were as follows: 1 H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.43-7.28 (m, 4H), 7.21 (d, J=1.4Hz, 4H), 6.98-6. 53 (m, 6H), 2.64 (t, J=15.7Hz, 4H), 1.80-1.44 (m, 4H), 1.44-1.13 (m, 8H), 1.06-0.63 (m, 6H).

[0088] Example 7: Synthesis of representative compound T-6

[0089] The synthesis method is as follows:

[0090]

[0091] The specific steps are as follows:

[0092] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 4.0 g (20 mmol) of 4-hexylphenylacetonitrile (T-6-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether with a volume ratio of 2:1 as the eluent to obtain a red solid (compound T-6).

[0093] The yield of compound T-6 was approximately 79%; its structural analysis results were as follows: 1 H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.49-7.27 (m, 4H), 7.21 (d, J=1.5Hz, 4H), 7.01-6.5 4(m, 6H), 2.64(t, J=15.5Hz, 4H), 1.85-1.45(m, 4H), 1.30-1.11(m, 10H), 1.00-0.55(m, 6H).

[0094] Example 8: Synthesis of representative compound T-7

[0095] The synthesis method is as follows:

[0096]

[0097] The specific steps are as follows:

[0098] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 5.1 g (20 mmol) of 4-decylphenylacetonitrile (T-7-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-7).

[0099] The yield of compound T-7 was approximately 75%; its structural analysis results are as follows: 1H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.44-7.32 (m, 4H), 7.21 (d, J=1.4Hz, 4H), 6.86-6.77 (m, 4H), 6 .74 (t, J=1.4Hz, 2H), 2.64 (t, J=15.7Hz, 4H), 1.81-1.46 (m, 4H), 1.36-1.04 (m, 29H), 1.08-0.71 (m, 6H).

[0100] Example 9: Synthesis of representative compound T-8

[0101] The synthesis method is as follows:

[0102]

[0103] The specific steps are as follows:

[0104] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 6.5 g (20 mmol) of 4-pentadecanoylphenylacetonitrile (T-8-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product obtained is purified by silica gel column chromatography using dichloromethane / petroleum ether with a volume ratio of 2:1 as the eluent to obtain a red solid (compound T-8).

[0105] The yield of compound T-8 was approximately 72%; its structural analysis results are as follows: 1 H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.42-7.33 (m, 4H), 7.21 (d, J=1.4Hz, 4H), 6.87-6.76 (m, 4H), 6 .74 (t, J=1.4Hz, 2H), 2.64 (t, J=15.5Hz, 4H), 1.83-1.42 (m, 4H), 1.38-1.11 (m, 48H), 1.01-0.64 (m, 6H).

[0106] Example 10: Synthesis of representative compound T-9

[0107] The synthesis method is as follows:

[0108]

[0109] The specific steps are as follows:

[0110] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 8.0 g (20 mmol) of 4-eicosylphenylacetonitrile (T-9-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product obtained is purified by silica gel column chromatography using dichloromethane / petroleum ether with a volume ratio of 2:1 as the eluent to obtain a red solid (compound T-9).

[0111] The yield of compound T-9 was approximately 83%; its structural analysis results were as follows: 1 H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.38 (d, J = 7.5Hz, 4H), 7.21 (s, 4H), 6.82 (d, J = 7.5Hz, 4H) , 6.74 (s, 2H), 2.64 (t, J=7.9Hz, 4H), 1.63 (p, J=7.8Hz, 4H), 1.37-1.08 (m, 68H), 0.97-0.64 (m, 6H).

[0112] Example 11 Synthesis of representative compound T-10

[0113] The synthesis method is as follows:

[0114]

[0115] The specific steps are as follows:

[0116] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 2.7 g (20 mmol) of 4-fluorophenylacetonitrile (T-10-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether with a volume ratio of 2:1 as the eluent to obtain a red solid (compound T-10).

[0117] The yield of compound T-10 was approximately 84%; its structural analysis results are as follows: 1 H NMR (500MHz, Chloroform) δ7.75 (s, 2H), 7.43-7.23 (m, 8H), 7.21 (d, J=1.4Hz, 4H), 6.74 (t, J=1.4Hz, 2H).

[0118] Example 12 Synthesis of representative compound T-11

[0119] The synthesis method is as follows:

[0120]

[0121] The specific steps are as follows:

[0122] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 2.8 g (20 mmol) of 4-cyanophenylacetonitrile (T-11-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product obtained is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-11).

[0123] The yield of compound T-11 was approximately 76%; its structural analysis results are as follows: 1 H NMR (500MHz, Chloroform) δ 8.07-7.94 (m, 4H), 7.75 (s, 2H), 7.62-7.49 (m, 4H), 7.21 (d, J=1.4Hz, 4H), 6.74 (t, J=1.4Hz, 2H).

[0124] Example 13 Synthesis of representative compound T-12

[0125] The synthesis method is as follows:

[0126]

[0127] The specific steps are as follows:

[0128] Weigh 3.6 g (10 mmol) of aldehyde-containing intermediate (4) and 3.2 g (20 mmol) of phenylacetonitrile (T-12-1) and add them to 50 mL of anhydrous ethanol and stir to dissolve. Under nitrogen protection, add 2.0 g of sodium hydroxide as an alkaline catalyst and heat under reflux overnight (about 10 h). After the reaction is complete, cool to room temperature and a large amount of reddish-brown precipitate will precipitate. Filter and collect the filter cake and wash it 2-3 times with anhydrous ethanol to remove impurities. After drying, the crude product is purified by silica gel column chromatography using dichloromethane / petroleum ether at a volume ratio of 2:1 to obtain a red solid (compound T-12).

[0129] The yield of compound T-12 was approximately 79%; its structural analysis results were as follows: 1H NMR (500MHz, Chloroform) δ 8.29-8.11 (m, 4H), 8.04 (s, 2H), 7.72-7.55 (m, 4H), 7.21 (d, J=1.4Hz, 4H), 6.74 (t, J=1.4Hz, 2H).

[0130] Application examples

[0131] 1. Device fabrication

[0132] The tetracyananthracene derivatives with dual-terminal substitution structures prepared in Examples 2-13 of this invention can be used as semiconductor active layer materials for organic field-effect transistors (OFETs). The devices can be fabricated using conventional structures such as bottom-gate-top contact (BGTC) and top-gate-bottom contact (TGBC). The basic process flow is as follows:

[0133] (1) Substrate cleaning and pretreatment: Using heavily doped silicon wafers / 200nm SiO2 as the substrate, the substrate is ultrasonically cleaned with acetone, isopropanol and deionized water in sequence, dried and baked at 120-150℃ to remove residual moisture; if necessary, the dielectric layer surface is modified by self-assembly such as HMDS to improve surface wettability.

[0134] (2) Active layer deposition: The tetracyanane derivatives (compounds T-1 to T-12) with double-terminal substituted structures prepared in Examples 2-13 of the present invention were dissolved in chlorobenzene (1.0 wt%), filtered through a 0.2 μm filter membrane, and then spin-coated at 2000 rpm to form a film. After spin-coating, the film was annealed in a nitrogen atmosphere at 100 °C for 30 min to improve the crystallinity and surface smoothness of the film.

[0135] (3) Electrode formation: Au source and drain electrodes (thickness of about 40 nm) are deposited on the active layer by thermal evaporation. The channel length L = 50 μm and the width W = 1000 μm. After the device is completed, it is sealed with UV-cured epoxy resin and encapsulated with glass sheet in a nitrogen glove box.

[0136] 2. Performance Testing

[0137] The extracted electron mobility μ was measured using a conventional semiconductor parameter analyzer (Agilent B1500) under a nitrogen atmosphere at room temperature. e Threshold voltage V th , On / off current ratio Ion / Ioff and air stability (migration retention rate after being placed in air for 30 days).

[0138] The test results are shown in the table below:

[0139]

[0140]

[0141] As can be seen from the table above, the embodiments of the present invention achieve a comprehensive technical effect of improved mobility, reduced threshold voltage and enhanced air stability through the regulation of terminal groups, confirming that this series of materials can be used as high-performance n-type OFET semiconductors.

[0142] The above embodiments are merely examples of several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention patent.

[0143] It should be noted that those skilled in the art can make various modifications and improvements without departing from the inventive concept, and these all fall within the scope of protection of this invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A tetracyananthracene derivative having a dual-terminal substituted structure, characterized in that, Its general structural formula is as follows: R is selected from -F, -NO2, -CN, or C. n H 2n+1 (n is an integer between 0 and 20) 2. The tetracyananthracene derivative with a double-terminal substituted structure according to claim 1, characterized in that, It is any of the following compounds:

3. The method for preparing the tetracyananthracene derivative with a double-terminal substituted structure according to claim 1 or 2, characterized in that, Includes the following steps: S1. Weigh 2,6-dibromoanthraquinone and malononitrile according to the proportion, add them to an alcohol solvent, stir until completely dissolved under a nitrogen atmosphere, heat under reflux in the presence of an alkaline catalyst, and after cooling to room temperature, a yellow precipitate is formed to obtain 2,6-dibromotetracyanoanthracene compound. S2. Dissolve the 2,6-dibromotetracyanoanthracene compound in an organic solvent, and slowly and uniformly add a DMF / POCl3 mixture while stirring under ice-water bath conditions. After the addition is complete, stir at room temperature to allow the Vilsmeier reaction to occur, and obtain an aldehyde-containing intermediate. S3. The aldehyde-containing intermediate obtained in step S2 is condensed with an aryl acetonitrile compound with the desired terminal substitution structure under alkaline catalyst catalysis to introduce conjugated vinyl bridging units at both ends of the molecule, thereby obtaining a tetracyananthracene derivative with a double-terminal substitution structure.

4. The method for preparing the tetracyananthracene derivative with a dual-terminal substituted structure according to claim 3, characterized in that, In step S2, The organic solvent is dry tetrahydrofuran, preferably corresponding to 0.1 mol of 2,6-dibromotetracyanoanthracene compound, and the amount of dry tetrahydrofuran used is 1000 mL; And / or, in the DMF / POCl3 mixture, the volume ratio of DMF to POCl3 is 1:1, preferably, corresponding to 0.1 mol of 2,6-dibromotetracyanoanthracene compound, the amount of DMF / POCl3 mixture added is 100 mL; And / or, the addition rate of the DMF / POCl3 mixture is controlled by a dropping time of 30-40 min; And / or, the reaction time of the Vilsmeier reaction is 4-6 hours.

5. The method for preparing the tetracyananthracene derivative with a double-terminal substituted structure according to claim 4, characterized in that, In step S2, It also includes post-treatment of the aldehyde-containing intermediates obtained from the Vilsmeier reaction; The post-processing specifically involves the following steps: after the Vilsmeier reaction is completed, the mixture is concentrated under reduced pressure, the residue is quenched with ice water and extracted with ethyl acetate, the organic phases are combined, dried over anhydrous sodium sulfate, concentrated by rotary evaporation, and then purified by silica gel column chromatography. Preferably, the eluent for the silica gel column chromatography is petroleum ether / ethyl acetate at a volume ratio of 5:

1.

6. The method for preparing the tetracyananthracene derivative with a dual-terminal substituted structure according to claim 3, characterized in that, In step S3, The condensation reaction is a Wittig-Horner or Knoevenagel condensation reaction, and the reaction time is 8-12 hours. And / or, the alkaline catalyst is any one of piperidine, ammonium acetate, and sodium hydroxide.

7. The method for preparing the tetracyananthracene derivative with a double-terminal substituted structure according to claim 6, characterized in that, In step S3, It also includes purifying the product of the condensation reaction. Specifically, after the condensation reaction is completed, the product is cooled to room temperature, the precipitated reddish-brown precipitate is collected, washed 2-3 times with anhydrous ethanol and dried, and finally purified by silica gel column chromatography with dichloromethane / petroleum ether as the eluent in a volume ratio of 2:

1.

8. The method for preparing the tetracyananthracene derivative with a double-terminal substituted structure according to claim 3, characterized in that, In step S1, The alcohol solvent is at least one of anhydrous ethanol, methanol, isopropanol, and ethylene glycol; The alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium hydride; The reaction time for the heating reflux reaction is 8-15 hours.

9. The method for preparing the tetracyananthracene derivative with a double-terminal substituted structure according to claim 8, characterized in that, In step S1, It also includes purifying the precipitated yellow precipitate by recrystallization using ethyl acetate / petroleum ether at a volume ratio of 1:2.5-4 as the recrystallization solvent.

10. The application of the tetracyananthracene derivative with a dual-terminal substituted structure as described in claim 1 or 2, or the tetracyananthracene derivative with a dual-terminal substituted structure prepared by any one of claims 3-9, in organic field-effect transistors.

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