A material for N-type photosensitive field-effect transistors based on naphthalenetetraimide

Abstract

This invention relates to an N-type photosensitive field-effect transistor material based on naphthalenetetraimide, with the general structural formula [formula omitted], wherein R is alkyl, benzyl, substituted benzyl, aryl, or substituted aryl, and X is O or S. The N-type photosensitive field-effect transistor material of this invention exhibits high mobility and strong light response performance, as well as excellent photosensitivity, providing a material basis for the research and application of photosensitive sensors.

Description

Technical Field

[0001] This invention belongs to the field of transistor material technology, specifically relating to an N-type photosensitive field-effect transistor material based on naphthalenetetraimide. Background Technology

[0002] Since the 1970s, when American physicist Alan J. Heeger, American chemist Alan G. MacDiarmid, and Japanese chemist Hideki Shirakawa first discovered that iodine-doped polyacetylene possesses metallic properties, breaking the traditional notion that organic compounds are non-conductive, this discovery ushered in the era of organic semiconductor materials research. Over the past few decades, organic semiconductor materials have been widely used in the electronics field. Organic field-effect transistors (OFETs) based on organic semiconductor materials, due to their many characteristics different from inorganic transistors, especially their potential applications in flexible electronic devices, have become one of the hot topics in molecular materials research. Organic semiconductor materials, as active-layer transistor devices, offer advantages over traditional inorganic semiconductor devices, such as lower cost, large-area fabrication, and integration with flexible substrates, attracting widespread attention worldwide. Over the past two decades, research on organic semiconductor materials has made significant progress. The most important performance indicator of transistors, mobility, has reached or surpassed the level of amorphous silicon (Q-Si:H) transistors, demonstrating enormous market potential and industrial application prospects in the field of organic electronic devices, particularly in flexible displays, sensors, complementary circuits, memory, RFID tags, and electronic paper. Therefore, exploring the use of organic semiconductor materials as active layer materials for OFET devices is an inevitable trend with significant research value and application prospects. Currently, research on organic semiconductor materials mainly focuses on the molecular design of high carrier mobility, while research on field-effect transistors with photosensitive properties is very insufficient, especially regarding N-type organic semiconductor materials with photosensitive properties.

[0003] Naphthalenetetramethyldiimide (NDI) is a classic N-type semiconductor core material used in organic field-effect transistor (OFET) devices, exhibiting high carrier mobility. Furthermore, reports on sulfoxocarbonyl (C=S)-substituted carbonyl (C=O) compounds are scarce. Sulfur, as a group-agent of oxygen, possesses similar chemical and physical properties, and sulfur-containing compounds are an important class of semiconductor materials with excellent optoelectronic properties. Studies on sulfoxocarbonyl (C=S) naphthalenetetramethyldiimide (NDI) are limited, and research on the photosensitivity of this material is even less.

[0004] Indigo / semi-indigo is a dye molecule that has long been widely used in the pigment industry. Could this traditional commercial material structure be applied to the emerging semiconductor industry? Semi-indigo molecules can undergo luminescent isomerization under light radiation; the carbon-carbon double bonds in the semi-indigo structure can undergo Z-type and E-type transitions under different light irradiations. (See references: Bull. Chem. Soc. Jpn, 1992, 65, 649-656, Bull. Chem. Soc. Jpn, 1992, 65, 657-663, Chemical Physics Letters 428(2006) 167–173). Its configurational transformations are shown below:

[0005]

[0006] However, there are currently no reports on the design and synthesis of N-type semiconductor materials with high mobility and strong photoresponse properties by combining semithioindole molecules with classic N-type naphthalenetetrahydride (NDI) and thionaphthalenetetrahydride. Summary of the Invention

[0007] In view of the above-mentioned situation in the prior art, the present invention proposes an N-type photosensitive field-effect transistor material containing a half-thioindene structure and naphthalenetetrahydride or thionaphthalenetetrahydride (hereinafter referred to as naphthalenetetrahydride-based N-type photosensitive field-effect transistor material). By combining the good semiconductor properties of the classic N-type semiconductor material structure naphthalenetetrahydride (NDI) or thionaphthalenetetrahydride, the excellent semiconductor device performance of sulfur-containing compounds, and the characteristic that half-thioindene molecules can undergo configurational transformation under specific light conditions, the naphthalenetetrahydride-based N-type photosensitive field-effect transistor material proposed in this invention has high mobility and strong light response performance.

[0008] According to the present invention, an N-type photosensitive field-effect transistor material based on naphthalenetetraimide is proposed, the general structural formula of which is as follows:

[0009]

[0010] R can be alkyl, benzyl, substituted benzyl, aryl or substituted aryl, etc., and X can be O or S.

[0011] Furthermore, R is preferably C1 to C2. 20 (i.e., alkyl groups having 1 to 20 carbon atoms), more preferably C4 to C5. 12 Alkyl groups (i.e., alkyl groups with 4 to 12 carbon atoms).

[0012] Furthermore, R is preferably phenyl.

[0013] Furthermore, the preferred structural formula for R is... Where n is 5 to 10.

[0014] Furthermore, R is preferably benzyl.

[0015] Furthermore, the preferred structural formula for R is... Where n is 1 to 20.

[0016] Furthermore, the preferred structural formula for R is... Where n is 1 to 20, more preferably n is 2 to 10.

[0017] Furthermore, the preferred structural form of R1 is... Where n is 1 to 20.

[0018] This invention combines the excellent semiconductor properties of naphthalenetetradiimide (NDI), a classic N-type semiconductor material, with the superior semiconductor device performance of sulfur-containing compounds, and the configurational transformation of hemithioindole molecules under specific light conditions. A new N-type photosensitive field-effect transistor material based on naphthalenetetradiimide is designed and synthesized. This material exhibits high mobility, strong light response, and excellent photosensitivity, providing a material foundation for the research and application of photosensitive sensors. Detailed Implementation

[0019] To better understand the purpose, technical solution, and advantages of this invention, the following detailed description is provided in conjunction with embodiments.

[0020] This invention proposes an N-type photosensitive field-effect transistor material based on naphthalenetetraimide (NDI) or thionaphthalenetetraimide, which combines the excellent semiconductor properties of classic N-type semiconductor materials, the superior semiconductor device properties of sulfur-containing compounds, and the configurational transformation of hemithioindole molecules under specific light conditions. The material of this invention has high mobility and strong light response performance.

[0021] The structural formula of the material of this invention is as follows:

[0022]

[0023] R and X are as described above.

[0024] When X is 0, the general formula for synthesis is as follows:

[0025]

[0026] Step 1: 1-Benzothiophene-3(2H)-one (I in the above general formula) was dissolved in benzene, and an equivalent amount of 4-(BOC-amino)benzaldehyde (II in the above general formula) and a catalytic amount of piperidine were added. The mixture was heated to reflux, and the reaction was monitored by thin-layer chromatography until complete. A saturated aqueous solution of ammonium chloride was added, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and dried to obtain the intermediate BOC-amino-substituted semithioindigo (III in the above general formula).

[0027] Step 2: Remove the BOC group from the BOC-amino-substituted semithioindole (III) obtained in Step 1 under trifluoroacetic acid conditions to obtain the intermediate amino-substituted semithioindole (IV in the above general formula).

[0028] Step 3: Tetramethyl 1,4,5,8-naphthocarboxylate (V in the above general formula) was heated under glacial acetic acid and concentrated hydrochloric acid to give a monoacid anhydride compound (VI in the above general formula).

[0029] Step 4: The amino-substituted semithioindole (IV) obtained in step 2 is reacted with the monoacid anhydride compound (VI) obtained in step 3 to obtain the naphthimide derivative (VII in the above general formula);

[0030] Step 5: The naphthylene derivative (VII) obtained in step 4 is heated under trifluoroacetic acid conditions to obtain the acid anhydride compound (VIII in the above general formula);

[0031] Step 6: React the acid anhydride compound (VIII) obtained in step 5 with various amine compounds to obtain the target compound, naphthalimide containing a hemithioindole structural unit (T in the above general formula).

[0032] Example 1: Synthesis of representative compound T1

[0033] Compound T1 The synthetic route is shown below:

[0034]

[0035] 30 g (0.2 mol) of 1-benzothiophene-3(2H)-one (I) was dissolved in 300 mL of benzene, and 44.2 g (0.2 mol) of 4-(BOC-amino)benzaldehyde (II) and 1 g of piperidine were added. The mixture was heated under reflux for 5 h, and the reaction was monitored by thin-layer chromatography until complete. 300 mL of saturated ammonium chloride aqueous solution was added, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and dried to obtain 62.3 g of BOC-amino-substituted semithioindigo (III).

[0036] 1H NMR (500MHz, CDCl3) δ8.35 (s, 1H), 8.23–8.16 (m, 2H), 7.99–7.89 (m, 2H), 7.84–7.74 (m, 3H), 7.61 (td, J = 14.9, 3.2Hz, 1H), 7.50 (s, 1H), 1.49 (s, 9H).

[0037] 52.9 g of BOC-amino-substituted semithioindigo(III) was dissolved in 200 mL of dichloromethane and 100 mL of trifluoroacetic acid. The mixture was stirred at room temperature for 30 minutes. After removing excess trifluoroacetic acid with a saturated sodium carbonate washing solution, the mixture was concentrated and dried. The crude product was separated by column chromatography to obtain the target product 32.5 g of amino-substituted semithioindigo(IV).

[0038] 1 H NMR (500MHz, CDCl3) δ8.35(s,1H),8.00–7.85(m,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),6.48–6.35(m,2H).

[0039] 65.6 g (0.2 mol) of tetramethyl 1,4,5,8-naphthalenetetracarboxylate (V) was dissolved in 250 mL of glacial acetic acid and 50 mL of concentrated hydrochloric acid. The mixture was heated and stirred at 120 °C for 12 hours. The solution was then concentrated under reduced pressure to remove the residue, yielding 50.2 g of the intermediate compound monoacid anhydride compound (VI).

[0040] 1 H NMR (500MHz, CDCl3) δ8.87 (d, J = 15.0 Hz, 2H), 8.68 (d, J = 15.0 Hz, 2H), 3.90 (s, 6H).

[0041] 31.4 g (0.1 mol) of monoacid anhydride compound (VI), 30.4 g (0.12 mol) of amino-substituted hemithioindole (IV), 5.05 g (0.05 mol) of triethylamine, and 6.1 g (0.05 mol) of benzoic acid were dissolved in 300 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 48.5 g of the target intermediate compound, naphthimide derivative (VII).

[0042] 1H NMR(500MHz, CDCl3)δ8.73(d,J=15.0Hz,2H),8.39(d,J=15.0Hz,2H),8.35(s,1H),8.23–8.16(m,2H),8.00 –7.89(m,2H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.37–7.28(m,2H),3.90(s,6H).

[0043] 43.8 g (0.08 mol) of naphthimide derivative (VII) was dissolved in 200 mL of trifluoroacetic acid, heated and stirred at 80 °C for 24 hours, the solution was concentrated under reduced pressure and separated by column chromatography to obtain 30.2 g of acid anhydride compound (VIII).

[0044] 1 H NMR (500MHz, CDCl3) δ8.91(d,J=7.5Hz,2H),8.76(d,J=7.5Hz,2H),8.35(s,1H),8.20(d,J=7.4H z,2H),7.99–7.87(m,2H),7.83–7.73(m,1H),7.61(td,J=7.5,1.5Hz,1H),7.33(d,J=7.5Hz,2H).

[0045] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 4.38 g (0.06 mol) of n-butylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 15.4 g of the target compound (T1).

[0046] 1 H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.25–8.14(m,2H),8.01–7.88(m,2H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14 .9,3.2Hz,1H),7.39–7.27(m,2H),3.13(t,J=14.9Hz,2H),1.54(pd,J=14.9,1.5Hz,2H),1.39–1.13(m,2H),0.90(t,J=13.0Hz,3H).

[0047] Example 2: Synthesis of representative compound T2

[0048] The synthetic route for compound T2 is shown below:

[0049]

[0050] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 6.06 g (0.06 mol) of n-hexylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 14.5 g of the target compound (T2).

[0051] 1 H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.24–8.14(m,2H),7.99–7.88(m,2H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J= 14.9,3.2Hz,1H),7.38–7.28(m,2H),3.14(t,J=15.2Hz,2H),1.67(pd,J=15.0,0.6Hz,2H),1.41–1.06(m,6H),0.99–0.70(m,3H).

[0052] Example 3: Synthesis of representative compound T3

[0053] The synthetic route for compound T3 is shown below:

[0054]

[0055] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 7.75 g (0.06 mol) of n-octylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 17.5 g of the target compound (T3).

[0056] 1 H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.24–8.15(m,2H),7.99–7.89(m,2 H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.36–7.29(m,2H).

[0057] Example 4: Synthesis of representative compound T4

[0058] The synthetic route for compound T4 is shown below:

[0059]

[0060] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 10.86 g (0.06 mol) of n-dodecaneamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane, heated under reflux and stirred for 2 hours, concentrated under reduced pressure to remove solvent, and separated by column chromatography to obtain 16.3 g of the target compound (T4).

[0061] 1 H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.24–8.15(m,2H),7.99–7.87(m,2H),7.83–7.74(m,1H),7.61(td,J=15.0, 3.2Hz,1H),7.37–7.28(m,2H),3.14(t,J=15.1Hz,2H),1.67(qd,J=15.5,0.6Hz,2H),1.39–1.10(m,18H),0.99–0.77(m,3H).

[0062] Example 5: Synthesis of representative compound T5

[0063] The synthetic route for compound T5 is shown below:

[0064]

[0065] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 5.58 g (0.06 mol) of aniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 13.4 g of the target compound (T5).

[0066] 1 H NMR(500MHz, CDCl3)δ8.62(s,8H),8.35(s,2H),8.25–8.15(m,4H),8.00–7.88(m,4H), 7.79(dd,J=15.3,3.0Hz,2H),7.66–7.52(m,8H),7.48–7.39(m,4H),7.36–7.28(m,4H).

[0067] Example 6: Synthesis of representative compound T6

[0068] The synthetic route for compound T6 is shown below:

[0069]

[0070] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 10.6 g (0.06 mol) of 4-hexylaniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 12.5 g of the target compound (T6).

[0071] 1 H NMR(500MHz, CDCl3)δ8.61(s,4H),8.34(s,1H),8.23–8.13(m,2H),7.98–7.86(m,2H),7.82–7.72(m,1H),7.60(td,J=14.9,3.1Hz,1H),7 .44–7.36(m,2H),7.36–7.28(m,2H),7.21–7.10(m,2H),2.52(t,J=15.7Hz,2H),1.72–1.47(m,2H),1.41–1.19(m,4H),1.03–0.77(m,3H).

[0072] Example 7: Synthesis of representative compound T7

[0073] The synthetic route for compound T7 is shown below:

[0074]

[0075] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 12.3 g (0.06 mol) of 4-octylaniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 13.7 g of the target compound (T7).

[0076] 1H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.24–8.16(m,2H),7.99–7. 87(m,2H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.44 –7.38(m,2H),7.36–7.28(m,2H),7.20–7.12(m,2H),2.52(t,J=12.1Hz,2H) ,1.63(ttd,J=15.1,11.9,0.8Hz,2H),1.38–1.12(m,9H),1.02–0.69(m,3H).

[0077] Example 8: Synthesis of the representative compound T8

[0078] The synthetic route for compound T8 is shown below:

[0079]

[0080] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 13.98 g (0.06 mol) of p-decylaniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 11.2 g of the target compound (T8).

[0081] 1 H NMR (500MHz, CDCl3) δ8.62(s,4H),8.35(s,1H),8.25–8.16(m,2H),7.94(ddd,J=15.2,7.6,5.0Hz,2H),7.79(dd,J=15.3,3.0Hz,1H),7.62(dd,J=14.9, 3.2Hz,1H),7.45–7.38(m,2H),7.37–7.28(m,2H),7.21–7.11(m,2H),2.52( t,J=15.7Hz,2H),1.77–1.46(m,2H),1.34–1.13(m,15H),0.99–0.78(m,3H).

[0082] Example 9: Synthesis of representative compound T9

[0083] The synthetic route for compound T9 is shown below:

[0084]

[0085] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 6.42 g (0.06 mol) of benzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 14.3 g of the target compound (T9).

[0086] 1 H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.25–8.13(m,2H),8.01–7.87(m,2H),7. 79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.41–7.15(m,7H),4.34(s,2H).

[0087] Example 10: Synthesis of representative compound T10

[0088] The synthetic route for compound T10 is shown below:

[0089]

[0090] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 8.1 g (0.06 mol) of 4-ethylbenzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 15.3 g of the target compound (T10).

[0091] 1 H NMR (500MHz, CDCl3) δ8.62(s,4H),8.35(s,1H),8.24–8.14(m,2H),7.99–7.87(m,2H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14. 9,3.2Hz,1H),7.37–7.28(m,2H),7.27–7.20(m,2H),7.12–7.01(m,2H),4.34(s,2H),2.72(q,J=13.2Hz,2H),1.18(t,J=13.2Hz,3H).

[0092] Example 11: Synthesis of representative compound T11

[0093] The synthetic route for compound T11 is shown below:

[0094]

[0095] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 12.3 g (0.06 mol) of 4-heptylbenzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 17.6 g of the target compound (T11).

[0096] 1 H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.23–8.14(m,2H),8.00–7.88(m ,2H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.37–7.28(m,2 H),7.27–7.19(m,2H),7.15–7.02(m,2H),4.34(s,2H),2.59(t,J=11.8Hz,2H),1 .63(dddd,J=15.1,12.5,11.7,5.6Hz,2H),1.39–1.07(m,8H),1.05–0.68(m,3H).

[0097] Example 12: Synthesis of the representative compound T12

[0098] The synthetic route for compound T12 is shown below:

[0099]

[0100] 25.2 g (0.05 mol) of acid anhydride compound (VIII), 14.82 g (0.06 mol) of 4-decylbenzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 18.3 g of the target compound (T12).

[0101] 1H NMR(500MHz, CDCl3)δ8.62(s,4H),8.35(s,1H),8.24–8.14(m,2H),8.00–7 .88(m,2H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.3 7–7.29(m,2H),7.28–7.19(m,2H),7.13–7.01(m,2H),4.34(s,2H),2.59(t ,J=15.6Hz,2H),1.78–1.46(m,2H),1.39–1.10(m,14H),0.99–0.67(m,3H).

[0102] When X is S, the general formula for synthesis is as follows:

[0103]

[0104] Step 1: 1-Benzothiophene-3(2H)-one (I in the above general formula) was dissolved in benzene, and an equivalent amount of 4-(BOC-amino)benzaldehyde (II in the above general formula) and a catalytic amount of piperidine were added. The mixture was heated to reflux, and the reaction was monitored by thin-layer chromatography until complete. A saturated aqueous solution of ammonium chloride was added, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and dried to obtain the intermediate BOC-amino-substituted semithioindigo (III in the above general formula).

[0105] Step 2: Remove the BOC group from the BOC-amino-substituted semithioindole (III) obtained in Step 1 under trifluoroacetic acid conditions to obtain the intermediate amino-substituted semithioindole (IV in the above general formula).

[0106] Step 3: Tetramethyl 1,4,5,8-naphthalenetetrathiocarboxylate (V in the above general formula) was heated under glacial acetic acid and concentrated hydrochloric acid to give thiomonoacid anhydride compound (VI in the above general formula).

[0107] Step 4: The amino-substituted hemithioindole (IV) obtained in step 2 is reacted with the thiomonoacid anhydride compound (VI) obtained in step 3 to obtain the thionaphthaleneimide derivative (VII in the above general formula);

[0108] Step 5: The thionaphthalene amide derivative (VII) obtained in step 4 is heated under trifluoroacetic acid conditions to obtain the thioanhydride compound (VIII in the above general formula);

[0109] Step 6: The thioanhydride compound (VIII) obtained in step 5 is reacted with various amine compounds to obtain the target compound, thionaphthalene diimide containing a hemithioindole structural unit (T in the above general formula).

[0110] Example 13: Synthesis of representative compound T13

[0111] Compound T13 The synthetic route is shown below:

[0112]

[0113] 30 g (0.2 mol) of 1-benzothiophene-3(2H)-one (I) was dissolved in 300 mL of benzene, and 44.2 g (0.2 mol) of 4-(BOC-amino)benzaldehyde (II) and 1 g of piperidine were added. The mixture was heated under reflux for 5 h, and the reaction was monitored by thin-layer chromatography until it was complete. 300 mL of saturated ammonium chloride aqueous solution was added, and the mixture was extracted three times with ethyl acetate. The organic phases were combined and dried to obtain 62.3 g of BOC-amino-substituted semithioindigo (III).

[0114] 1 H NMR (500MHz, CDCl3) δ8.35 (s, 1H), 8.23–8.16 (m, 2H), 7.99–7.89 (m, 2H), 7.84–7.74 (m, 3H), 7.61 (td, J = 14.9, 3.2Hz, 1H), 7.50 (s, 1H), 1.49 (s, 9H).

[0115] 52.9 g of BOC-amino-substituted semithioindigo(III) was dissolved in 200 mL of dichloromethane and 100 mL of trifluoroacetic acid. The mixture was stirred at room temperature for 30 minutes. After removing excess trifluoroacetic acid with a saturated sodium carbonate washing solution, the mixture was concentrated and dried. The crude product was separated by column chromatography to obtain the target product 32.5 g of amino-substituted semithioindigo(IV).

[0116] 1 H NMR (500MHz, CDCl3) δ8.35(s,1H),8.00–7.85(m,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),6.48–6.35(m,2H).

[0117] 84.8 g (0.2 mol) of tetramethyl 1,4,5,8-naphthiotetracarboxylate (V) was dissolved in 300 mL of glacial acetic acid and 60 mL of concentrated hydrochloric acid. The mixture was heated and stirred at 120 °C for 24 hours. The solution was then concentrated under reduced pressure to remove the residue, yielding 61.5 g of the intermediate compound thiomonoacid anhydride (VI).

[0118] 1 H NMR (500MHz, CDCl3) δ7.83 (s, 4H), 3.46 (s, 6H).

[0119] 37.8 g (0.1 mol) of thiomonoacid anhydride compound (VI), 30.4 g (0.12 mol) of amino-substituted hemithioindole (IV), 5.05 g (0.05 mol) of triethylamine, and 6.1 g (0.05 mol) of benzoic acid were dissolved in 300 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 41.3 g of the target intermediate compound, thionaphthaleneimide derivative (VII).

[0120] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.22–8.12(m,2H),8.00–7.89(m,2H),7.86(s,4H),7. 79(dd,J=15.3,3.1Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.28–7.15(m,2H),3.47(s,6H).

[0121] 49.1 g (0.08 mol) of thionaphthaleneimide derivative (VII) was dissolved in 200 mL of trifluoroacetic acid, heated and stirred at 80 °C for 24 hours, the solution was concentrated under reduced pressure to remove the solution, and separated by column chromatography to obtain 35.2 g of thioanhydride compound (VIII).

[0122] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.21–8.10(m,2H),7.99–7.89(m,2H),7.86(s,4 H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.30–7.17(m,2H).

[0123] 28.4 g (0.05 mol) of thioanhydride compound (VIII), 4.38 g (0.06 mol) of n-butylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 21.5 g of the target compound (T13).

[0124] 1H NMR(500MHz, CDCl3)δ8.35(s,1H),8.22–8.10(m,2H),8.00–7.89(m,2H),7.86(s,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14 .9,3.2Hz,1H),7.28–7.14(m,2H),3.65(t,J=14.8Hz,2H),1.48(pd,J=14.6,2.0Hz,2H),1.38–1.21(m,2H),0.90(t,J=12.9Hz,3H).

[0125] Example 14: Synthesis of the representative compound T14

[0126] The synthetic route for compound T14 is shown below:

[0127]

[0128] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 6.06 g (0.06 mol) of n-hexylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 21.5 g of the target compound (T14).

[0129] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.21–8.12(m,2H),8.01–7.90(m,2H),7.86(s,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61(t d,J=14.9,3.2Hz,1H),7.27–7.16(m,2H),3.65(t,J=14.9Hz,2H),1.78–1.47(m,2H),1.40–1.12(m,6H),0.99–0.75(m,3H).

[0130] Example 15: Synthesis of representative compound T15

[0131] The synthetic route for compound T15 is shown below:

[0132]

[0133] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 7.75 g (0.06 mol) of n-octylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 18.7 g of the target compound (T15).

[0134] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.20–8.13(m,2H),7.98–7.90(m,2H),7.86(s,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61(t d,J=14.9,3.2Hz,1H),7.27–7.15(m,2H),3.65(t,J=14.9Hz,2H),1.83–1.45(m,2H),1.39–1.10(m,10H),1.02–0.77(m,3H).

[0135] Example 16: Synthesis of the representative compound T16

[0136] The synthetic route for compound T16 is shown below:

[0137]

[0138] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 10.86 g (0.06 mol) of n-dodecaneamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 19.4 g of the target compound (T16).

[0139] 1 H NMR(500MHz, CDCl3)δ8.33(s,1H),8.19–8.09(m,2H),7.97–7.88(m,2H),7.84(s,4H),7.77(dd,J=15.3,3.0Hz,1H),7.59(t d,J=14.9,3.2Hz,1H),7.24–7.13(m,2H),3.64(t,J=14.9Hz,2H),1.77–1.46(m,2H),1.39–1.12(m,18H),1.06–0.70(m,3H).

[0140] Example 17: Synthesis of the representative compound T17

[0141] The synthetic route for compound T17 is shown below:

[0142]

[0143] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 5.58 g (0.06 mol) of aniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 18.5 g of the target compound (T17).

[0144] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.21–8.11(m,2H),8.00–7.89(m,2H),7.86(s,4H), 7.79(dd,J=15.3,3.0Hz,1H),7.66–7.48(m,4H),7.36–7.29(m,2H),7.27–7.16(m,2H).

[0145] Example 18: Synthesis of representative compound T18

[0146] The synthetic route for compound T18 is shown below:

[0147]

[0148] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 10.6 g (0.06 mol) of 4-hexylaniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 16.4 g of the target compound (T18).

[0149] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.22–8.12(m,2H),7.99–7.89(m,2H),7.86(s,4H),7.79(dd,J=15.3,3.0H z,1H),7.61(td,J=14.9,3.2Hz,1H),7.29–7.08(m,6H),2.52(s,2H),1.63(s,2H),1.34(s,4H),0.91(s,3H).

[0150] Example 19: Synthesis of representative compound T19

[0151] The synthetic route for compound T19 is shown below:

[0152]

[0153] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 12.3 g (0.06 mol) of 4-octylaniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 15.3 g of the target compound (T19).

[0154] 1 H NMR (500MHz, CDCl3) δ8.34(s,1H),8.20–8.11(m,2H),7.99–7.88(m,2H),7.85(s,4H),7.78(dd,J=15.4,3.1Hz,1H),7.60(td,J=14.9 ,3.2Hz,1H),7.26–7.16(m,4H),7.16–7.09(m,2H),2.52(t,J=11.4Hz,2H),1.76–1.45(m,2H),1.44–1.10(m,9H),1.00–0.75(m,3H).

[0155] Example 20: Synthesis of representative compound T20

[0156] The synthetic route for compound T20 is shown below:

[0157]

[0158] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 13.98 g (0.06 mol) of p-decylaniline, 2.53 g (0.025 mol) of triethylamine, and 3.0 g (0.025 mol) of benzoic acid were dissolved in 200 mL of dry N,N-dimethylformamide. The mixture was heated and stirred at 100 °C for 12 h. The solvent was removed by concentration under reduced pressure, and the residue was separated by column chromatography to obtain 21.5 g of the target compound (T20).

[0159] 1H NMR(500MHz, CDCl3)δ8.35(s,1H),8.22–8.12(m,2H),8.00–7.89(m,2H),7.86(s,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9 ,3.2Hz,1H),7.26–7.17(m,4H),7.17–7.07(m,2H),2.52(t,J=12.5Hz,2H),1.78–1.47(m,2H),1.41–1.12(m,15H),1.03–0.72(m,3H).

[0160] Example 21: Synthesis of representative compound T21

[0161] The synthetic route for compound T21 is shown below:

[0162]

[0163] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 6.42 g (0.06 mol) of benzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 16.5 g of the target compound (T21).

[0164] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.22–8.11(m,2H),7.99–7.89(m,2H),7.86(s,4H),7. 79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz,1H),7.41–7.15(m,7H),4.45(s,2H).

[0165] Example 22: Synthesis of representative compound T22

[0166] The synthetic route for compound T22 is shown below:

[0167]

[0168] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 8.1 g (0.06 mol) of 4-ethylbenzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 17.8 g of the target compound (T22).

[0169] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.21–8.12(m,2H),8.01–7.89(m,2H),7.86(s,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61( td,J=14.9,3.2Hz,1H),7.30–7.16(m,4H),7.13–7.00(m,2H),4.45(s,2H),2.72(q,J=13.2Hz,2H),1.18(t,J=13.2Hz,3H).

[0170] Example 23: Synthesis of representative compound T23

[0171] The synthetic route for compound T23 is shown below:

[0172]

[0173] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 12.3 g (0.06 mol) of 4-heptylbenzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 22.4 g of the target compound (T23).

[0174] 1 H NMR(500MHz, CDCl3)δ8.33(s,1H),8.20–8.10(m,2H),7.98–7.88(m,2H),7.84(s,4H),7.77(dd,J=15.3,3.1Hz,1H),7.59(td,J=15.0,3.2H z,1H),7.27–7.15(m,4H),7.12–6.97(m,2H),4.44(s,2H),2.59(t,J=11.8Hz,2H),1.79–1.46(m,2H),1.38–1.10(m,9H),1.00–0.71(m,3H).

[0175] Example 24: Synthesis of representative compound T24

[0176] The synthetic route for compound T24 is shown below:

[0177]

[0178] 28.4 g (0.05 mol) of acid anhydride compound (VIII), 14.82 g (0.06 mol) of 4-decylbenzylamine, and 7.74 g (0.06 mol) of N,N-diisopropylethylamine were dissolved in 200 mL of 1,4-dioxane and heated under reflux for 2 hours. The solvent was removed by concentration under reduced pressure, and the product was separated by column chromatography to obtain 15.4 g of the target compound (T24).

[0179] 1 H NMR(500MHz, CDCl3)δ8.35(s,1H),8.20–8.11(m,2H),7.99–7.89(m,2H),7.86(s,4H),7.79(dd,J=15.3,3.0Hz,1H),7.61(td,J=14.9,3.2Hz ,1H),7.27–7.16(m,4H),7.12–7.02(m,2H),4.45(s,2H),2.59(t,J=1 5.5Hz,2H),1.77–1.49(m,2H),1.36–1.10(m,14H),1.04–0.77(m,3H).

[0180] Fabrication of organic field-effect transistors

[0181] Cleaning and finishing of silicon wafers

[0182] The Si / SiO2 substrate was purchased directly, with a SiO2 thickness of 250 nm. The silicon wafer was ultrasonically cleaned for 10 min each with pure water, acetone, and isopropanol. After drying with nitrogen, it was irradiated with UV for 10 min to obtain a clean silicon wafer. Then, it was immersed in a 0.1 mol / L OTS(8) toluene solution at 65°C for 20 min. Afterward, it was cleaned with toluene to remove surface residue, dried with nitrogen, and the OTS-modified silicon wafer was obtained for later use.

[0183] Device fabrication and performance testing

[0184] A semiconductor mask is used to mask the silicon wafer, and a suitable substrate temperature is selected. The thin film is then fabricated under high vacuum. The vacuum level is approximately 2.0 × 10⁻⁶. -4 Pa, the evaporation rate of the semiconductor material (the semiconductor material obtained according to Examples 1-24 of the present invention) is controlled at... After thin film preparation, electrodes are deposited using an electrode mask, with Au as the electrode material. The Au electrode deposition rate is controlled at [value missing]. The fabricated devices had channel aspect ratios of 380μm / 38μm, 580μm / 58μm, 780μm / 78μm, and 980μm / 98μm. Semiconductor performance was tested using a Keithly 4200 semiconductor analyzer. Id-Vg and Id-Vd curves were measured under normal conditions and under UV illumination. Mobility was calculated using the formula below.

[0185] I d =(W / 2L)μ TFT C i (V g -V th ) 2

[0186] The switching ratio of the device is obtained based on the current ratio at 0V and -60V.

[0187] Device performance of representative semiconductor materials obtained according to the above embodiments 1-24 of the present invention:

[0188] Data for compound DPh-BTBF devices:

[0189]

[0190]

[0191] According to the table above, it can be seen from the mobility data under normal conditions and light radiation that the representative semiconductor materials obtained according to the above embodiments 1-24 of the present invention exhibit excellent photosensitivity.

Claims

1. An N-type photosensitive field-effect transistor material based on naphthalenetetraimide, the general structural formula of which is as follows: in, X is either O or S; R is an alkyl group having 1 to 20 carbon atoms; R is a phenyl group; The structural formula of R is: , where n is 5 to 10; R is benzyl; The structural formula of R is: , where n is 1 to 20; The structural formula of R is: , where n is 1 to 20; The structural formula of R is: , where n is 1 to 20.

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