Synthesis method of novel dithiazole imide monomer and derivative thereof

Abstract

The invention provides a synthesis method of a novel dithiazole imide monomer and a derivative thereof. The structural formula of the compound is # imgabs0 #, wherein R1 is C1-18 alkyl; r2 is substitution of electron donating / withdrawing groups such as halogen atoms, alkenyl, aromatic hydrocarbon or heterocyclic aromatic hydrocarbon in different proportions. According to the invention, thiourea and dibromobutanedione are taken as raw materials, a dibromo-dithiazole imide monomer is synthesized through six steps, and unsaturated hydrocarbons such as alkenyl, aryl or heterocyclic aryl are coupled through Suzuki or stille reaction to obtain a series of small molecular luminescent materials. The micromolecules can be applied to the fields of identification and sensing, biological imaging, anti-counterfeiting technology, organic light-emitting diodes and other optoelectronic devices.

Description

Technical Field

[0001] This invention belongs to the field of organic semiconductor materials, specifically relating to the synthesis of a novel dithiazolyl imide monomer, as well as the synthesis methods and properties of a series of functionalized dithiazolyl imide compounds. These compounds exhibit luminescent properties and can serve as the light-emitting layer or electron / hole transport layer of organic light-emitting diodes. They can also be used in fields such as identification and sensing, bioimaging, and anti-counterfeiting technology. Background Art

[0002] In recent years, with the in-depth study of organic optoelectronic materials, a large number of novel conjugated electron acceptor molecules have been developed. Aromatic imides are one of the most important electron acceptors. Due to their strong electron-withdrawing ability, the ability of N substituents to enhance solubility and influence molecular aggregation behavior, and the ease of functionalization through derivatization of the aromatic core, they have found widespread application in flexible optoelectronic devices, chemical sensors, and supramolecular assemblies.

[0003] The properties of aromatic imides depend largely on their π-conjugated cores. By introducing different groups, the lowest unoccupied molecular orbital (LUMO) of aromatic imides can be adjusted to give them different electrical properties. Since seven-membered ring aromatic imides have good flexibility and can be fused with different aromatic rings, thereby regulating intramolecular interactions and frontier orbital energy levels, they have gradually attracted people's attention. In 2008, the Marks group designed and synthesized dithiophene imide (BTI). Compared with six-membered ring imide building blocks such as naphthalene diimide (NDI) and perylene diimide (PDI), the BTI receptor building block not only effectively reduces steric hindrance, has good planarity and close molecular spacing, but also has strong electron-withdrawing ability. Therefore, the design and synthesis of new BTI-based polymers provides an excellent opportunity for the development of high-performance n-type semiconductors and has opened up a design boom for seven-membered ring aromatic imides. Among them, dithiazolyl imide (BTzI) has received widespread attention since it was first synthesized in 2018, and has been used in various organic optoelectronic devices. Its structure is

[0004] At present, the application of BTzI derivatives is mainly focused on the research of BTzI-based polymers in organic field effect transistors (OFETs) and organic solar cells (OSCs), while the application of BTzI-based small molecules as luminescent materials has been rarely reported. By isomerizing the nitrogen and sulfur elements in the BTzI structural unit to form a new monomer dithiazolyl imide (iBTzI), the nitrogen atom is smaller than the sulfur atom, which is conducive to a more planar aromatic imide, and is conducive to intermolecular stacking and charge transfer, which is expected to fill the gap in its application in the field of luminescent materials. The structure of iBTzI is Where R1 is C 1～18 alkyl.

[0005] The present invention realizes the synthesis of iBzTI structural units and develops a series of functionalized iBTzI compounds, which are expected to become a new type of potential luminescent functional materials. Summary of the Invention

[0006] The object of the present invention is to provide a method for synthesizing iBTzI monomer and its derivatives.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention synthesizes a dibromodithiazolyl imide monomer through six steps. The dithiazolyl imide monomer is then used as the main component for structural modification. A flexible alkyl chain is introduced to improve its solubility. A color-enhancing group or chromophoric group, such as an aromatic ring, is introduced to increase the conjugation length, thereby increasing the delocalization capacity of the π system electron cloud, thereby improving electron transport capacity and fluorescence quantum efficiency. This modifies its chemical properties, solubility, luminescence performance, and electronic properties, improving its application performance, and designing and synthesizing a series of iBTzI derivatives. The general reaction formula is as follows:

[0009]

[0010] Where R1 is C 1～18 Alkyl; X of the iBTzI monomer is a halogen atom, preferably bromine; R2 of the iBTzI derivative is substituted with electron donating / withdrawing groups such as halogen atoms, alkenyl, aryl or heteroaryl in different proportions, and the preferred structure is as follows:

[0011]

[0012] The synthesis method of the iBTzI monomer and its derivatives of the present invention specifically comprises the following steps: using thiourea and dibromobutanedione as raw materials, 1) synthesizing a thiazole ring through a Hantzsch thiazole synthesis method, 2) replacing the amino group with bromine through a Sandmeyer reaction, 3) introducing an ester group through a Knochel-Hauser base, 4) hydrolyzing the ester group, 5) dehydration condensation of a dicarboxylic acid, and 6) imidization reaction to synthesize a dibromodithiazolyl imide monomer, and then coupling unsaturated hydrocarbons such as alkenyl, aryl, or heteroaryl groups through a Suzuki or Stille reaction to obtain a series of iBTzI derivatives.

[0013] Beneficial Effects: The synthesis method of the present invention offers advantages such as readily available raw materials, low cost, high yield, and scalable mass production at gram scale. The synthesized series of iBTzI derivatives exhibit high thermal stability and high luminescence intensity, and hold great promise for development in optoelectronic devices such as identification and sensing, bioimaging, anti-counterfeiting technology, and organic light-emitting diodes. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0015] Figure 1 The UV-visible absorption spectrum of 7c-7h in toluene solution (c = 1.0 × 10 -5 mol L -1 )

[0016] Figure 2 The fluorescence emission spectrum of 7c-7h in toluene solution (c = 1.0 × 10 -5 mol L -1 ) DETAILED DESCRIPTION

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter relates.

[0018] The present invention will be further described below with reference to the following embodiments, but the present invention is not limited to these examples.

[0019] Example 1:

[0020] Taking the synthesis of N-isopentyl-dibromodithiazolyl imide as an example, its structure is as follows:

[0021]

[0022] Step 1: Synthesis of 2,2'-diamino-4,4'-bithiazole (1)

[0023] The reaction formula is as follows:

[0024]

[0025] Thiourea (6.384 g, 84 mmol) and dibromobutanedione (9.760 g, 40 mmol) were dissolved in chromatography-grade methanol (80 mL) and reacted overnight at 50°C. After the reaction, the methanol was removed and saturated sodium carbonate solution was added. The mixture was stirred, filtered, and dried under vacuum to yield 7.795 g of 2,2'-diamino-4,4'-bithiazole (98% yield).

[0026] The spectral data of the obtained product are as follows:

[0027] 1 H NMR(400MHz,DMSO-d6)δ6.12(s,4H),5.71(s,2H). 13 C NMR(101MHz,DMSO-d6)δ168.61,146.76,102.83.

[0028] Step 2: Synthesis of 2,2'-dibromo-4,4'-bithiazole (2)

[0029] The reaction formula is as follows:

[0030]

[0031] 2,2'-Diamino-4,4'-bithiazole (3.960 g, 20 mmol) was dissolved in a 20 mL:20 mL:20 mL mixture of concentrated sulfuric acid, concentrated phosphoric acid, and 40% fluoroboric acid at 0°C. An 8 mL aqueous solution of sodium nitrite (3580 g, 52 mmol) at 0°C was slowly added dropwise. After a 2-hour reaction, the reaction mixture was transferred to an 80 mL aqueous solution of sodium bromide (10.7 g, 104 mmol) and copper sulfate (8.320 g, 52 mmol) at 0°C and stirred for 3 hours. After the reaction, the mixture was filtered, and the resulting filter cake was mixed with magnesium sulfate and dichloromethane, sonicated, and then washed with water. The crude product was separated by column chromatography to yield 3.501 g of 2,2'-dibromo-4,4'-bithiazole in a 54% yield.

[0032] The spectral data of the obtained product are as follows:

[0033] 1 H NMR (400MHz, CHCl3-d) δ7.75 (s, 2H). 13 C NMR(101MHz,CHCl3-d)δ149.63,136.85,119.47.

[0034] Step 3: Synthesis of diethyl 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylate (3)

[0035]

[0036] Under anhydrous and oxygen-free conditions, 2,2'-dibromo-4,4'-bithiazole (978 mg, 3 mmol) was dissolved in redistilled tetrahydrofuran (30 mL). A solution of TMPMgCl·LiCl (18 mmol) in tetrahydrofuran (18 mL) was slowly added dropwise at -40°C. After 4.5 hours of reaction, ethyl cyanoformate (18 mmol) was added and the mixture was allowed to warm to room temperature for 22 hours. After completion of the reaction, dichloromethane and water were added for extraction. The organic phase was dried and separated by column chromatography to obtain 1.040 g of diethyl 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylate, in a yield of 74%.

[0037] The spectral data of the obtained product are as follows:

[0038] 1H NMR (400MHz, CHCl3-d) δ4.21 (q, J = 7.1Hz, 4H), 1.22 (t, J = 7.1Hz, 6H). 13 C NMR(101MHz,CHCl3-d)δ159.42,150.16,140.47,131.73,62.21,14.05.

[0039] Step 4: Synthesis of 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid (4)

[0040]

[0041] To a reaction flask containing diethyl 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylate (1.004 g, 2.1 mmol), tetrahydrofuran (6.4 mL) and water (6.4 mL) were added, followed by lithium hydroxide (153 mg, 6.4 mmol). The mixture was stirred at 50°C overnight. After the reaction, the tetrahydrofuran was removed, concentrated hydrochloric acid was added, and the mixture was filtered. The filter cake was vacuum dried to yield 884 mg of 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid, for an 88% yield.

[0042] The spectral data of the obtained product are as follows:

[0043] 1 H NMR (400 MHz, DMSO-d6) δ 13.98. 13 C NMR(101MHz,DMSO-d6)δ160.88,149.58,140.08,133.50.

[0044] Step 5: Synthesis of dibromodithiazolyl anhydride (5)

[0045]

[0046] Acetic anhydride (6 mL) was added to a reaction flask containing 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid (828 mg, 2 mmol) and the mixture was stirred and refluxed at 120°C overnight. After the reaction, the mixture was filtered and dried under vacuum to obtain 626 mg of dibromobithiazole anhydride (a yield of 78%).

[0047] The spectral data of the obtained product are as follows:

[0048] 13 C NMR (101MHz, CHCl3-d) δ151.36, 147.71, 147.20, 131.76.

[0049] Step 6: Synthesis of N-isopentyl-dibromodithiazolyl imide (6)

[0050]

[0051] Chloroform (20 mL) was added to a reaction flask containing dibromodithiazole anhydride (788 mg, 2 mmol), followed by a chloroform solution (10 mL) of isoamylamine (191 mg, 2.2 mmol) and refluxed at 60°C for 2 hours. After the reaction was complete, the chloroform was dried, dibromosulfoxide (6 mL) was added, and the mixture was stirred and refluxed at 130°C for 3 hours. After the reaction was complete, dichloromethane and water were added for extraction, and the organic phase was dried and separated by column chromatography to obtain 511 mg of N-isoamyl-dibromodithiazole imide in a yield of 55%.

[0052] The spectral data of the obtained product are as follows:

[0053] 1 H NMR (400MHz, CHCl3-d) δ4.17–4.08(m,2H),1.70–1.60(m,J=13.2,6.5Hz,1H),1.56–1.45(m,2H),0.94(d,J=6.5Hz,6H). 13 C NMR (101MHz, CHCl3-d) δ158.09,146.13,145.18,138.66,44.70,35.89,26.64,22.50.

[0054] Example 2:

[0055] Taking the synthesis of N-isopentyl-monobromo-monovinyldithiazole imide (7a) as an example, its structure is as follows:

[0056]

[0057] The raw materials used and their synthesis methods are:

[0058]

[0059] Under anaerobic conditions, N-isobutyl-dibromodithiazolyl imide (45.1 mg, 0.1 mmol), vinylboronic acid pinacol ester (15.4 mg, 0.1 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) (6.5 mg, 0.08 mmol), and cesium carbonate (65.2 mg, 0.2 mmol) were dissolved in a mixture of toluene (2.7 mL) and water (0.3 mL) and heated under reflux at 100°C for 6 hours. After the reaction, dichloromethane and water were added for extraction. The organic phase was dried by spin drying and separated by column chromatography to obtain 42 mg of the product in a yield of 34%.

[0060] The spectral data of the obtained product are as follows:

[0061] 1 H NMR(400MHz,CHCl3-d)δ7.06(m,J=17.6,10.9Hz,1H),6.30(d,J=17.6Hz,1H),5.86(d,J =10.9Hz, 1H), 4.12 (d, J = 7.4Hz, 2H), 2.17 (m, J = 13.8, 7.0Hz, 1H), 0.95 (d, J = 6.7Hz, 6H).

[0062] Example 3:

[0063] Taking the synthesis of N-isopentyl-dithiophenedithiazolidine imide (7b) as an example, its structure is as follows:

[0064]

[0065] The raw materials used and their synthesis methods are:

[0066] 1) The raw materials used in the Suzuki coupling reaction and their synthesis methods are:

[0067]

[0068] Under anaerobic conditions, N-isopentyl-dibromodithiazolyl imide (186 mg, 0.4 mmol), 2-thiopheneboronic acid (154 mg, 1.2 mmol), potassium phosphate (339 mg, 1.6 mmol), and chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos Pd G2) (38 mg, 0.0048 mmol) were dissolved in a mixture of tetrahydrofuran (8 mL) and water (4 mL) and heated under reflux at 50°C for 3 hours. After the reaction, dichloromethane and water were added for extraction. The organic phase was dried by rotary evaporation and separated by column chromatography to obtain 151 mg of N-isopentyl-dithiophenedithiazolyl imide in an 80% yield.

[0069] The spectral data of the obtained product are as follows:

[0070] 1 H NMR (400MHz, CHCl3-d) δ7.78 (d, J = 3.7Hz, 2H), 7.59 (d, J = 5.1Hz, 2H), 7.17 (dd, J = 5.0, 3. 8Hz,2H),4.35–4.19(m,2H),1.79–1.67(m,1H),1.65–1.58(m,2H),1.01(d,J=6.5Hz,6H). 13 C NMR (101MHz, CHCl3-d) δ168.15,159.20,146.75,135.92,134.41,131.14,130.03,128.51,44.69,36.14,26.74,22.55.

[0071] 2) The raw materials used in the Stille coupling reaction and their synthesis methods are:

[0072]

[0073] Under anhydrous and oxygen-free conditions, N-isopentyl-dibromodithiazolyl imide (6) (46.5 mg, 0.1 mmol), 2-tri-n-butyltinthiophene (328 mg, 0.22 mmol), potassium phosphate, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) (9 mg, 0.012 mmol) were dissolved in toluene (5 mL) and heated under reflux at 110°C for 6 hours. After the reaction, potassium fluoride solution was added and stirred for 3 hours, followed by extraction with dichloromethane. The organic phase was dried by rotary evaporation and separated by column chromatography to obtain 40 mg of N-isopentyl-dithiophenedithiazolyl imide (7b) in a yield of 85%.

[0074] The spectral data of the obtained product are as follows:

[0075] 1 H NMR (400MHz, CHCl3-d) δ7.78 (d, J = 3.7Hz, 2H), 7.59 (d, J = 5.1Hz, 2H), 7.17 (dd, J = 5.0, 3. 8Hz,2H),4.35–4.19(m,2H),1.79–1.67(m,1H),1.65–1.58(m,2H),1.01(d,J=6.5Hz,6H). 13 C NMR (101MHz, CHCl3-d) δ168.15,159.20,146.75,135.92,134.41,131.14,130.03,128.51,44.69,36.14,26.74,22.55.

[0076] Example 4:

[0077] Taking the synthesis of N-isobutyl-bis(4-(9-carbazolyl)phenyl)dithiazolyl imide (7c) as an example, its structure is as follows:

[0078]

[0079] The raw materials used and their synthesis methods are:

[0080]

[0081] Under anaerobic conditions, N-isobutyl-dibromodithiazolyl imide (22.5 mg, 0.05 mmol), bis(4-(9-carbazolyl)phenyl)boronic acid (NBAPC) (36 mg, 0.125 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) (6 mg, 0.0075 mmol) and potassium phosphate (42 mg, 0.2 mmol) were dissolved in a mixed solution of toluene (2.7 mL) and water (0.3 mL) and heated under reflux at 100°C for 6 hours. After the reaction, dichloromethane and water were added for extraction. The organic phase was dried by rotary evaporation and separated by column chromatography to obtain 34 mg of the product with a yield of 88%. The maximum ultraviolet absorption wavelength (λ abs max ) is 340, 359 nm (Note: all measured in toluene solution), the maximum fluorescence emission wavelength (λ em max ) is 458nm (Note: all measurements were made in toluene solution), the fluorescence quantum yield (Φ FL ) is 28.1% (Note: Φ FL is the absolute fluorescence quantum yield of the film doped with 0.1wt% PMMA), thermal decomposition temperature (Td ) is 470℃ (Note: T d (Thermal weight loss 5% temperature). UV absorption spectrum is attached. Figure 1 , fluorescence emission spectrum is attached Figure 2 .

[0082] The spectral data of the obtained product are as follows:

[0083] 1 H NMR (400MHz, CHCl3-d) δ8.44(d,J=8.5Hz,4H),8.16(d,J=7.7Hz,4H),7.80(d,J=8.4Hz,4H),7.52(d,J=8.2Hz,4H), 7.48–7.40(m,4H),7.33(t,J=7.4Hz,4H),4.24(d,J=7.3Hz,2H),2.28(m,J=13.3,7.0Hz,1H),1.04(d,J=6.7Hz,6H). 13 C NMR(101MHz,CHCl3-d)δ173.43,159.81,147.28,141.35,140.37,135.52,130.91 ,129.22,127.30,126.30,123.94,120.69,120.56,109.83,52.10,27.38,20.45.

[0084] Example 5:

[0085] Taking the synthesis of N-isobutyl-bis(4-(diphenylamino)phenyl)dithiazolyl imide (7d) as an example, its structure is as follows:

[0086]

[0087] The raw materials used and their synthesis methods are:

[0088] The synthesis method is as shown in Example 4. The boric acid reagent used is 4-(diphenylamino)phenylboronic acid. The yield is 80%. em max is 496nm, Φ FL 44.3%, T d is 419℃. See the attached UV absorption spectrum Figure 1 , fluorescence emission spectrum is attached Figure 2 .

[0089] The spectral data of the obtained product are as follows:

[0090] 1H NMR(400MHz,CHCl3-d)δ7.97(d,J=8.8Hz,4H),7.37–7.28(m,8H),7.15(m,J=18.0,7.4Hz,12H), 7.06(d,J=8.8Hz,4H), 4.17(d,J=7.3Hz,2H), 2.23(m,J=13.7,6.8Hz,1H), 0.98(d,J=6.8Hz,6H). 13 C NMR (101MHz, CHCl3-d) δ174.38,159.91,151.39,147.44,146.62,133.78,129.71,128.82,125.88,124.95,124.61,120.84,51.88,27.33,20.47.

[0091] Example 6:

[0092] Taking the synthesis of N-isobutyl-bis(4-(1,2,2-triphenylvinyl)phenyl)dithiazole imide (7e) as an example, its structure is as follows:

[0093]

[0094] The raw materials used and their synthesis methods are:

[0095] The synthesis method thereof refers to Example 4, and the boric acid reagent used is (4-(1,2,2-triphenylvinyl)phenyl)boric acid, with a yield of 89%, λ em max 505nm, Φ FL 50.1%, T d is 431℃. See the attached UV absorption spectrum Figure 1 , fluorescence emission spectrum is attached Figure 2 .

[0096] The spectral data of the obtained product are as follows:

[0097] 1 H NMR (400MHz, CHCl3-d) δ7.88 (d, J = 8.1Hz, 4H), 7.16-7.04 (m, 34H), 4.17 (d, J = 7.3Hz, 2H), 2.22 (m, J = 13.7, 6.9Hz, 1H), 0.98 (d, J = 6.7Hz, 6H). 13CNMR(101MHz,CHCl3-d)δ174.52,159.84,148.19,147.23,143.34,143.26,143.10,142.70,139.91,134.6 8,132.15,131.47,131.42,131.39,130.15,128.06,127.99,127.82,127.08,126.90,51.95,27.31,20.44.

[0098] Example 7:

[0099] Taking the synthesis of N-isobutyl-bis(4-(10H-phenoxazin-10-yl)phenyl)dithiazolyl imide (7f) as an example, its structure is as follows:

[0100]

[0101] The raw materials used and their synthesis methods are:

[0102] The synthesis method is as described in Example 4. The boric acid reagent used is 10-(4-boronic acid pinacol ester phenyl) phenoxazine. The yield is 84%. em max 628nm, Φ FL 44.2%, T d is 426℃. See the attached UV absorption spectrum Figure 1 , fluorescence emission spectrum is attached Figure 2 .

[0103] The spectral data of the obtained product are as follows:

[0104] 1 H NMR(400MHz,CHCl3-d)δ8.43–8.33(m,4H),7.56(d,J=8.3Hz,4H),6.76–6.54(m,12H), 5.95(d,J=7.9Hz,4H),4.21(d,J=7.3Hz,2H),2.33–2.21(m,1H),1.03(d,J=6.6Hz,6H). 13 C NMR(101MHz,CHCl3-d)δ173.25,159.80,147.19,144.01,142.57,135.75,133.72 ,132.17,131.84,130.30,123.36,121.89,115.80,113.29,52.15,27.40,20.53.

[0105] Example 8:

[0106] Taking the synthesis of N-isobutyl-bis((9,9-dimethyl-9,10-dihydroacridin-10-yl)phenyl)dithiazolyl imide (7g) as an example, its structure is as follows:

[0107]

[0108] The raw materials used and their synthesis methods are:

[0109] The synthesis method is as shown in Example 4. The boric acid reagent used is 10-(4-boronic acid pinacol ester phenyl)-9,9-dimethyl-9,10-dihydroacridine. The yield is 73%. em max 557nm, Φ FL 40.0%, T d is 395℃. See the attached UV absorption spectrum Figure 1 , fluorescence emission spectrum is attached Figure 2 .

[0110] The spectral data of the obtained product are as follows:

[0111] 1 H NMR(400MHz,CHCl3-d)δ8.43(d,J=8.5Hz,4H),7.53(d,J=8.5Hz,4H),7.48(m,J=7.4,1.9Hz,4H),7.05–6.9 2(m,8H),6.34(m,J=7.8,1.7Hz,4H),4.23(d,2H),2.35–2.23(m,1H),1.70(s,12H),1.04(d,J=6.7Hz,6H). 13 C NMR(101MHz,CHCl3-d)δ172.68,158.84,146.30,144.07,139.50,134.63,131.05,130.9 3,129.57,129.25,125.54,124.49,120.17,113.28,51.11,35.13,30.26,26.35,19.48.

[0112] Example 9:

[0113] Taking the synthesis of N-isobutyl-bis((9,9-diphenyl-9,10-dihydroacridin-10-yl)phenyl)dithiazolyl imide (7h) as an example, its structure is as follows:

[0114]

[0115] The raw materials used and their synthesis methods are:

[0116] The synthesis method is as shown in Example 4. The boric acid reagent used is 10-(4-boronic acid pinacol ester phenyl)-9,9-diphenyl-9,10-dihydroacridine. The yield is 68%, λ em max 528nm, Φ FL 40.1%, T d is 454℃. See the attached UV absorption spectrum Figure 1 , fluorescence emission spectrum is attached Figure 2 .

[0117] The spectral data of the obtained product are as follows:

[0118] 1 H NMR(400MHz,Methylene Chloride-d2)δ8.32(d,J=8.4Hz,4H),7.28(m,J=6.3,4.3,2.3Hz,16H),7.09(m,J=8.5,5.4,3.4Hz,4H),7.04–6.97(m,8 H),6.96–6.88(m,8H),6.52(d,J=8.2Hz,4H),4.19(d,J=7.3Hz,2H),2.23(m,J=13.3,6.6Hz,1H),1.00(d,J=6.7Hz,6H).

[0119] Table 1. List of spectral properties of 7c-7h

[0120]

Claims

1. A novel dithiazolyl imide compound, characterized in that The general structural formula is as follows: Where R1 is C 1～18 Alkyl; R2 is substituted with electron donating / withdrawing groups such as halogen atoms, alkenyl, aromatic hydrocarbons or heterocyclic aromatic hydrocarbons in different proportions.

2. An application of the novel dithiazolyl imide small molecule compound as claimed in claim 1, which can be used in the light-emitting layer or electron transport layer of an organic light-emitting diode, as well as in the fields of identification and sensing, bioimaging, anti-counterfeiting technology, etc.

3. The method for preparing the novel dithiazolyl imide monomer according to claim 1, characterized in that The specific steps of this method are: a. Dissolve thiourea and dibromobutanedione in chromatographic grade methanol and allow to react overnight at 50°C. After the reaction is complete, remove the methanol, add saturated sodium carbonate solution, stir, filter, and vacuum dry to obtain 2,2'-diamino-4,4'-bithiazole, whose structural formula is: b. Dissolve the 2,2'-diamino-4,4'-bithiazole obtained in step a in a 1mL:1mL:1mL mixed solution of concentrated sulfuric acid, concentrated phosphoric acid, and 40% fluoroboric acid at 0°C, and slowly add a 0°C aqueous solution of sodium nitrite. After reacting for 2 hours, transfer the reaction solution to a 0°C aqueous solution containing sodium bromide and copper sulfate and stir for 3 hours. After the reaction is completed, filter and mix the filter cake with magnesium sulfate and dichloromethane, sonicate, and wash with water. The crude product is separated by column chromatography to obtain 2,2'-dibromo-4,4'-bithiazole, whose structural formula is: c. Under anhydrous and oxygen-free conditions, dissolve the 2,2'-dibromo-4,4'-bithiazole obtained in step b in redistilled tetrahydrofuran. Slowly add a solution of TMPMgCl·LiCl in tetrahydrofuran dropwise at -40°C. After reacting for 4.5 hours, add ethyl cyanoformate and warm to room temperature for 22 hours. After the reaction, extract with dichloromethane and water. The organic phase is dried and separated by column chromatography to obtain diethyl 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylate, whose structural formula is: d. Add tetrahydrofuran and water to the reaction flask containing diethyl 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylate obtained in step c, then add lithium hydroxide and stir overnight at 50°C. After the reaction is complete, remove the tetrahydrofuran, add concentrated hydrochloric acid, and filter. The filter cake is vacuum dried to obtain the product 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid, whose structural formula is: e. Add acetic anhydride to the reaction flask containing 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid obtained in step d, and stir and reflux at 120°C overnight. After the reaction is completed, filter and vacuum dry to obtain the target product, dibromodithiazole anhydride, whose structural formula is: f. Add chloroform to the reaction flask containing the dibromodithiazolyl anhydride obtained in step e, then add the chloroform solution of amine to the reaction flask, and reflux at 60°C for 2 hours. After the reaction is complete, the chloroform is dried, dibromosulfoxide is added, and the mixture is stirred and refluxed at 130°C for 3 hours. After the reaction is complete, dichloromethane and water are added for extraction, the organic phase is dried, and column chromatography is performed to obtain N-alkyl-dibromodithiazolyl imide, where R2 is bromine and has the structural formula:

4. The novel dithiazolyl imide derivatization method according to claim 1, characterized in that The specific steps of this method are: 1) Suzuki coupling reaction method: Under anaerobic conditions, dibromodithiazolylimide, a boronic acid compound, a catalyst {[1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhosPd G2)}, and potassium phosphate are dissolved in a mixed solution (toluene / water or tetrahydrofuran / water) and heated under reflux at 100°C or 50°C for 3-6 hours. After the reaction, dichloromethane and water are added for extraction. The organic phase is dried by spin drying and separated by column chromatography to obtain functionalized iBTzI, whose structural formula is: 2) Stille coupling reaction method used: Under anhydrous and oxygen-free conditions, dibromodithiazolylimide, an organotin compound, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) were dissolved in toluene and heated under reflux at 110°C for 6 hours. After the reaction, potassium fluoride solution was added and stirred for 3 hours. Extraction was then performed with dichloromethane. The organic phase was dried and separated by column chromatography to obtain functionalized iBTzI, whose structural formula is:

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