Composition, organic fluorescent material, method for producing composition and method for producing thin film

Abstract

To provide a composition that allows for molding while maintaining excellent sensitivity in mechanochromic emission properties.SOLUTION: The present invention provides a composition represented by the following formula (1). In a formula (1), E1 is a following formula (2) or (3), and E2 is a phenyl group or a 1-naphthyl group that may have a specific substituent.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present invention relates to a composition, an organic fluorescent material, a method for producing the composition, and a method for producing a thin film. [Background technology]

[0002] Mechanochromic luminescent molecular crystals, which reversibly change the color of their fluorescent or phosphorescent light in response to mechanical stimuli such as rubbing or crushing, are expected to have a wide range of applications, mainly in the detection of pressure, strain, and wear, and are therefore expected to be used in pressure sensors, etc., and have been actively researched in recent years (Patent Document 1).

[0003] Patent Document 2 discloses a luminescent free-standing film obtained by forming a hybrid composition of organic nanocrystals and a polymer material. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6663820 [Patent Document 2] JP 2022-091772 A Summary of the Invention [Problem to be solved by the invention]

[0005] Conventionally, solid-state fluorescent organic molecules having mechanochromic luminescence properties are powder materials with non-uniform particle sizes, and therefore it has been difficult to mold and process them into desired shapes such as thin films unless they are combined with polymeric materials, etc. In addition, because the organic molecules are processed in combination with polymeric materials, etc., there is a risk that the sensitivity of the mechanochromic luminescence properties will decrease accordingly.

[0006] In view of the above problems, an object of the present invention is to provide a composition that can be molded while maintaining mechanochromic luminescence properties with good sensitivity. Another object of the present invention is to provide an organic fluorescent material using the composition, a method for producing the composition, and a method for producing a thin film. [Means for solving the problem]

[0007] The above problems are solved by the present invention, which is specified as follows. 1. A composition represented by the following formula (1): [ka] (In formula (1), E 1 is expressed by the following formula (2) or (3), and E 2 is expressed by the following formula (4) or (5). [ka] [ka] In formulas (2) to (5), R 1 ~R 2 , R 4 ~R 15 , R 17 ~R 32 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. 3 and R 16 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. 2. In the formula (1), E 1The composition according to item 1, wherein the compound is represented by the following formula (6), (7) or (23): [ka] (In formulas (6), (7), and (23), Ph is a phenyl group.) 3. In the formula (1), E 2 The composition according to 1 or 2 above, wherein the compound is represented by any one of the following formulas (8) to (12): [ka] 4. An organic fluorescent material comprising the composition according to any one of 1 to 3 above. 5. The organic fluorescent material according to 4 above, which is a fluorescent patterning material, a fluorescent switching material or a fluorescent sensor material. 6. A step of reacting a compound represented by the following formula (2') or (3') with a compound represented by the following formula (13) to prepare a compound represented by the following formula (2'') or (3''); A step of reacting a compound represented by the formula (2'') or (3'') with a compound represented by the following formula (4') or (5') to prepare a composition represented by the formula (1); 4. A method for producing the composition according to any one of 1 to 3 above, comprising the steps of: [ka] [ka] [ka] [ka] (In formula (13), formula (2'') or (3''), X 1 and X 2 are each, independently of one another, a leaving group used in a nucleophilic substitution reaction. 7. A step of dissolving the composition according to any one of 1 to 3 above in an organic solvent to prepare a solution of the composition; A step of adding a solution of the composition to a poor solvent for the composition, stirring the solution, and then filtering the solution through a filter; recovering the film of composition deposited on the filter after said filtration; The method for producing a thin film comprising the steps of: Effect of the Invention

[0008] According to the present invention, it is possible to provide a composition that can be molded while maintaining mechanochromic luminescence properties with good sensitivity. Furthermore, according to the present invention, it is possible to provide an organic fluorescent material using the composition, a method for producing the composition, and a method for producing a thin film. [Brief description of the drawings]

[0009] [Figure 1] 1 is a SEM image of the thin film of Example 1. [Diagram 2] PXRD patterns of the thin film and bulk crystal of Example 1. [Diagram 3] 1 is an emission spectrum of the thin film of Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Next, the embodiments for carrying out the present invention will be described in detail. It should be understood that the present invention is not limited to the following embodiments, and that appropriate changes and improvements in the design may be made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention.

[0011] <Composition> The composition according to this embodiment is represented by the following formula (1). [ka] (In formula (1), E 1 is expressed by the following formula (2) or (3), and E 2 is expressed by the following formula (4) or (5). [ka] [ka] In formulas (2) to (5), R 1 ~R 2 , R 4 ~R 15 , R 17 ~R 32 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. 3 and R 16 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

[0012] The composition according to the present embodiment has aromatic or heterocyclic rings with different electronic states at both ends of the ethylene glycol chain, and the aromatic or heterocyclic rings are stacked between molecules to form needle-shaped or fibrous microcrystals, which allows for processing as a deposit of entangled microcrystals. In addition, the mechanism by which the luminescence characteristics change is the phase transition from a crystalline state to an amorphous state due to mechanical stimulation, so that a thin film formed from the crystals of the composition maintains mechanochromic luminescence characteristics with good sensitivity.

[0013] The composition according to the present embodiment is a compound represented by the formula (1), 1 is preferably represented by the following formula (6), (7) or (23). With such a configuration, a crystal is formed in which intermolecular interactions are appropriately suppressed due to steric hindrance caused by the aryl group on the nitrogen atom, making it possible to perform molding processing while maintaining the mechanochromic luminescence properties. [ka] (In formulas (6), (7), and (23), Ph is a phenyl group.)

[0014] The composition according to the present embodiment is a compound represented by the formula (1), 2 is preferably represented by any one of the following formulae (8) to (12). According to this configuration, since the aromatic ring or heterocyclic ring has a structure different from those of the formulae (6), (7) and (23), it becomes easy to form needle-like or fibrous microcrystals by intermolecular stacking. In particular, E 2 The compositions represented by formulas (8) and (9) function as donor-acceptor type luminescent materials, and therefore exhibit mechanochromic luminescence properties, in which the luminescent color changes significantly when the phase transition from a crystalline state to an amorphous state occurs due to mechanical stimulation. [ka]

[0015] The composition according to this embodiment is preferably represented by any one of the following formulas (14) to (21) and (24). [ka]

[0016] <Method of producing the composition> Next, a method for producing the composition according to the present embodiment will be described in detail. The composition represented by formula (1) above comprises a step of reacting a compound represented by formula (2') or (3') below with a compound represented by formula (13) below to produce a compound represented by formula (2") or (3") below, and a step of reacting a compound represented by formula (2") or (3") below with a compound represented by formula (4') or (5') below to produce a composition represented by formula (1). [ka] [ka] [ka] [ka] (In formula (13), formula (2'') or (3''), X 1 and X 2 are each independently a leaving group, and are not particularly limited as long as they are a leaving group used in a nucleophilic substitution reaction. Preferred examples include, each independently a tosylate group (-OS(=O)2-CH4-CH3), a triflate group (-OS(=O)2-CF3), a mesylate group (-OS(=O)2-CH3), a nonafluorobutanesulfonate group (-OS(=O)2-CF9), a chloro group, a bromo group, an iodo group, a hydroxy group, and the like.

[0017] According to the method for producing the composition according to this embodiment, the composition according to this embodiment can be produced efficiently by a simple method.

[0018] <Method of manufacturing thin film> The method for producing a thin film according to this embodiment includes the steps of dissolving the composition according to this embodiment in an organic solvent to prepare a solution of the composition, adding the solution of the composition to a poor solvent for the composition and stirring it, and then filtering the solution through a filter, and recovering the thin film of the composition that has been deposited on the filter after filtration.

[0019] By adding a solution of the composition to a poor solvent for the composition and stirring it, the composition that is not soluble in the poor solvent is microcrystallized in the poor solvent. By suction-filtering the microcrystals of the composition with a filter, the microcrystals of the composition are deposited on the filter to form a thin film. This thin film can be easily recovered from the filter. As the filter, it is preferable to use a membrane filter. A membrane filter is used when removing fine particles in a solution, and can reliably capture particles larger than the pore size of the filter. Therefore, the microcrystals of the composition can be reliably captured and the microcrystals of the composition can be well deposited on the filter, and a thin film can be produced with good yield. Examples of organic solvents that dissolve the composition include chloroform, ethyl acetate, dichloromethane, and toluene. Examples of poor solvents for the composition include water, hexane, cyclohexane, acetonitrile, and methanol.

[0020] The thin film of the composition according to the present embodiment thus produced is composed of entangled needle-like or fibrous microcrystals made of the composition alone, and is therefore self-supporting, and the organic fluorescent material using the thin film has superior sensitivity in mechanochromic luminescence characteristics compared to that formed by doping a conventional polymer material.The thin film is also flexible and durable enough not to collapse under a certain stress.

[0021] In the above manufacturing method, a thin film is formed by depositing the composition on a filter, but the composition can be molded into the shape of a mold by suction filtration using a mold of a predetermined shape. In this way, the composition according to this embodiment can be molded into a free-standing molded product including a free-standing thin film of any shape while maintaining the mechanochromic luminescence properties. Such a free-standing molded product exhibits mechanochromic luminescence in which the luminescent color changes when a mechanical stimulus (such as rubbing with a spatula) is applied. In addition, by changing the substituent of the composition, the luminescent color and the response behavior to mechanical stimuli can be controlled and adjusted according to the application.

[0022] <Organic fluorescent materials> The composition according to the present embodiment can be used to prepare an organic fluorescent material having mechanochromic luminescence properties. The composition according to the present embodiment may be used alone to form an organic fluorescent material, or the composition according to the present embodiment may be doped into, for example, a polymeric material to prepare an organic fluorescent material. The organic fluorescent material formed by using the composition according to the present embodiment alone has a superior sensitivity of mechanochromic luminescence properties compared to that formed by doping into a polymeric material.

[0023] The organic fluorescent material according to this embodiment can be used, for example, as a fluorescent patterning material, a fluorescent switching material, or a fluorescent sensor material.

[0024] In addition, since the organic fluorescent material according to this embodiment has mechanochromic luminescence properties, it can be used in the following applications that utilize highly sensitive fluorescence detection. -Writable and erasable fluorescent memory material -Detection of stress and strain on deteriorated structures and partial strain in materials Wear detection in industrial machinery development Wearable tactile sensors -Detection of minute pressure applied to biomaterials EXAMPLES

[0025] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these.

[0026] <Example 1> (Synthesis of the composition of formula (14)) E 1 Triphenylimidazole, E 2 A composition represented by the above formula (14) having benzothiadiazole at the base was synthesized as follows. Under an argon atmosphere, a DMF solution (10 mL) of 4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol (1.0 mmol, 0.389 g) was added to a suspension (10 mL) of potassium carbonate (3.0 mmol, 0.414 g) ground in a mortar in N,N-dimethylformamide (DMF). After stirring at room temperature for 1 hour, a DMF solution (10 mL) of 1,2-bis(tosyloxy)ethane (3.0 mmol, 1.11 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were washed three times with water and once with saturated saline, and then dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the filtrate was evaporated under reduced pressure to obtain a crude product, which was then separated by silica gel column chromatography (dichloromethane / toluene / ethyl acetate=5:5:1) to obtain 2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (31), 0.411 g, yield 70%) as a white solid. The reaction formula is shown in formula (30) below. Next, under an argon atmosphere, a DMF solution (3.0 mL) of 4-(benzo[c][1,2,5]thiadiazol-4-yl)phenol (0.30 mmol, 0.0685 g) was added to a DMF solution (3.0 mL) of sodium hydride (55% in oil, 1.0 mmol, 0.0485 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (3.0 mL) of 2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (31), 0.30 mmol, 0.176 g) was added dropwise to the mixture, and the mixture was stirred at room temperature for 24 hours. Water was added to the reaction mixture, and the organic layer was separated. The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were washed five times with water and once with saturated saline, and then dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the filtrate was evaporated under reduced pressure to obtain a crude product, which was then separated by silica gel column chromatography (dichloromethane) and preparative thin layer chromatography (dichloromethane / toluene = 3:1) and recrystallized from toluene to obtain 4-(4-[2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethoxy]phenyl)benzo[c][1,2,5]thiadiazole (formula (14), 0.124 g, yield 64%) as yellow crystals. The reaction formula is shown in the following formula (32). [ka]

[0027] The melting point (Mp) of the composition of formula (14), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 212.8-214.8℃; IR (ATR): v max 3054, 1606, 1514, 1481, 1445, 1236, 1177, 1069, 942, 831 cm -1 ; 1H NMR (500 MHz, CDCl3): δ (ppm) 7.97 (dd, J = 8.2, 1.8 Hz, 1H), 7.92-7.88 (m, 2H), 7.69-7.64 (m, 2H), 7.61-7.59 (m, 2H), 7.38-7.34 (m, 2H), 7.31-7.18 (m, 9H), 7.13-7.09 (m, 4H), 7.05-7.03 (m, 2H), 6.85-6.83 (m, 2H), 4.41-4.34 (m, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 158.8, 158.5, 155.6, 153.5, 146.8, 138.0, 137.2, 134.5, 134.0, 131.1 (2C), 130.7, 130.5 (2C), 130.3 (2C), 130.2, 129.7, 129.0 (2C), 128.4 (2C), 128.3 (2C), 128.2, 128.1 (2C), 127.8, 127.4 (2C), 126.9, 126.5, 123.6, 119.9, 114.8 (2C), 114.2 (2C), 66.5, 66.3; HRMS-ESI (m / z): [M + H] + calcd for C 41 H 31 N4O2S, 643.2162; found, 643.2152.

[0028] (Casting of thin films of the composition of formula (14)) Concentration of the composition of formula (14): 2.5 × 10 -2 A chloroform solution of M was prepared. 250 μL of this was measured out using a microsyringe and added to 10 mL of hexane. The crystals were suspended by stirring at room temperature for 5 minutes, and then suction filtered through a membrane filter to recover the crystals. A thin film was obtained by peeling off the crystals that had accumulated in a film-like form on the membrane filter. An SEM image of the surface of the resulting thin film was taken. The SEM image is shown in Figure 1.

[0029] (Flexibility of thin film of composition of formula (14)) When one end of a thin film of the composition of formula (14) was held with tweezers and the other end was pressed, it could be bent easily without breaking, confirming that the film had good flexibility.

[0030] (Crystallization of thin film of composition of formula (14)) Powder X-ray diffraction measurements (PXRD) were performed under the same conditions for a thin film of the composition of formula (14) and a crystal (bulk crystal) of the composition of formula (14). The PXRD patterns obtained for each are shown in Figure 2. As shown in Figure 2, the PXRD pattern of the thin film showed good agreement with the PXRD pattern of the bulk crystal.

[0031] (Light Emitting Properties of Thin Films of the Composition of Formula (14)) When the surface of a thin film of the composition of formula (14) was stimulated by tracing it with a needle, the emission color changed while the thin film retained its shape. When it was subsequently heated to 200°C, the emission color disappeared and the film returned to its original state. The emission spectra of these films were measured. The results are shown in Figure 3.

[0032] <Example 2> (Synthesis of the composition of formula (18)) Under an argon atmosphere, a DMF solution (10 mL) of 4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenol (1.0 mmol, 0.386 g) was added to a DMF suspension (10 mL) of potassium carbonate (3.0 mmol, 0.414 g) ground in a mortar. After stirring at room temperature for 1 hour, a DMF solution (10 mL) of 1,2-bis(tosyloxy)ethane (3.0 mmol, 1.11 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the filtrate was evaporated under reduced pressure to obtain a crude product, which was then separated by silica gel column chromatography (dichloromethane / toluene / ethyl acetate = 6:6:1) to obtain 2-{4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (33), 0.517 g, yield 88%) as a white solid. The reaction formula is shown in the following formula (34). Next, under an argon atmosphere, a DMF solution (3.0 mL) of 4-(benzo[c][1,2,5]thiadiazol-4-yl)phenol (0.30 mmol, 0.0687 g) was added to a DMF suspension (3.0 mL) of sodium hydride (55% in oil, 1.0 mmol, 0.0424 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (3.0 mL) of 2-{4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (33), 0.30 mmol, 0.1757 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed three times with water and once with saturated saline, and then dried over anhydrous sodium sulfate. The drying agent was removed by filtration, toluene was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then separated by silica gel column chromatography (dichloromethane / ethyl acetate = 10:1, silica gel (60N, 15 g)) and preparative thin layer chromatography (chloroform) to obtain 4-(4-[2-{4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenoxy}ethoxy]phenyl)benzo[c][1,2,5]thiadiazole (formula (18), 0.120 g, yield 63%) as a yellow solid. The reaction formula is shown in the following formula (35).

[0033] [ka]

[0034] The melting point (Mp) of the composition of formula (18), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 200.4-204.0 ℃; IR (ATR): v max3065, 2962, 1606, 1511, 1450, 1378, 1237, 1178, 1058, 828 cm -1 ; 1 H NMR (500 MHz, CDCl3): δ (ppm) 8.87 (dd, J = 7.9, 1.0 Hz, 1H), 8.77 (d, J = 8.3 Hz, 1H), 8.71 (d, J = 8.3 Hz, 1H), 7.98-7.93 (m, 1H), 7.91-7.88 (m, 2H), 7.74 (t, J = 7.4 Hz, 1H), 7.67-7.58 (m, 6H), 7.54-7.48 (m, 5H), 7.26 (t, J = 7.3 Hz, 1H), 7.17 (d, J = 7.4 Hz, 1H), 7.11-7.08 (m, 2H), 6.90-6.86 (m, 2H), 4.39-4.33 (m, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 159.0, 158.8, 155.6, 153.5, 150.8, 138.8, 137.3, 134.0, 130.8 (2C), 130.5 (2C), 130.3, 130.1 (2C), 129.70, 129.68, 129.13 (2C), 129.07, 128.1, 127.9, 127.2 (2C), 127.0, 126.2, 125.5, 124.7, 124.0, 123.4, 123.1, 123.0, 122.7, 120.7, 119.9, 114.8 (2C), 114.3 (2C), 66.5, 66.4; HRMS-ESI (m / z): [M + H] + Calculate for C 41 H 29 N4O2S, 641.2006; found, 641.2013.

[0035] <Example 3> (Synthesis of the composition of formula (15)) Under an argon atmosphere, a DMF solution (1.0 mL) of 2-(4-hydroxyphenyl)anthraquinone (0.10 mmol, 0.0299 g) was added to a DMF suspension (1.0 mL) of sodium hydride (55% in oil, 1.0 mmol, 0.0414 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (1.0 mL) of 2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (31), 0.10 mmol, 0.0586 g) was added dropwise to the mixture, and the mixture was stirred at room temperature for 24 hours. Water was added to the reaction mixture, and the organic layer was separated. The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the filtrate was evaporated under reduced pressure to obtain a crude product, which was then separated by silica gel column chromatography (dichloromethane / toluene = 2:1) and preparative thin layer chromatography (dichloromethane / toluene = 4:1). The crude product was then recrystallized from toluene to obtain 2-(4-[2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethoxy]phenyl)anthracene-9,10-dione (formula (15), 0.043 g, yield 60%) as yellow crystals. The reaction formula is shown in formula (36) below.

[0036] [ka]

[0037] The melting point (Mp) of the composition of formula (15), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 231.6-232.3℃; IR (ATR): v max 3066, 1671, 1592, 1480, 1307, 1245, 1180, 1068, 948, 830cm -1 ; 1H NMR (500 MHz, CDCl3): δ (ppm) 8.51 (d, J = 2.0 Hz, 1H), 8.37-8.32 (m, 3H), 7.99 (dd, J = 8.3, 2.0 Hz, 1H), 7.84-7.79 (m, 2H), 7.72-7.68 (m, 2H), 7.61-7.58 (m, 2H), 7.39-7.36 (m, 2H), 7.29-7.16 (m, 9H), 7.14-7.11 (m, 2H), 7.09-7.03 (m, 4H), 6.86-6.83 (m, 2H), 4.39-4.33 (m, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 183.3, 182.9, 159.4, 158.5, 146.7, 146.3, 138.1, 137.2, 134.5, 134.2, 134.0, 133.9, 133.7, 133.6, 131.73, 131.70, 131.6, 131.1 (2C), 130.7, 130.5, 130.4 (2C), 129.1 (2C), 128.55 (2C), 128.46 (2C), 128.3 (2C), 128.17, 128.13 (2C), 128.07, 127.9, 127.4 (2C), 127.25, 127.18, 126.5, 124.9, 123.7, 115.3 (2C), 114.2 (2C), 66.6, 66.3; HRMS-ESI (m / z): [M + H] + Calculate for C 49 H 35 N2O4, 715.2591; found, 715.2581.

[0038] <Example 4> (Synthesis of the composition of formula (19)) Under an argon atmosphere, a DMF solution (3.0 mL) of 2-(4-hydroxyphenyl)anthraquinone (0.26 mmol, 0.0778 g) was added to a DMF suspension (3.0 mL) of sodium hydride (55% in oil, 0.91 mmol, 0.0395 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (3.0 mL) of 2-{4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (33), 0.26 mmol, 0.151 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, toluene was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then suction filtered while being washed with dichloromethane. The residue was recrystallized from toluene to obtain 2-(4-[2-{4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenoxy}ethoxy]phenyl)anthracene-9,10-dione (formula (19), 0.0681 g, yield 37%) as yellow crystals. The reaction formula is shown in formula (37) below.

[0039] [ka]

[0040] The melting point (Mp) of the composition of formula (19), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 245.8-246.6℃; IR (ATR): v max 3055, 2932, 1678, 1593, 1522, 1450, 1292, 1248, 1179, 1070, 942, 833 cm -1 ; 1H NMR (500 MHz, CDCl3): δ (ppm) 8.87 (dd, J = 8.0, 0.9 Hz, 1H), 8.77 (d, J = 8.3 Hz, 1H), 8.71 (d, J = 8.3 Hz, 1H), 8.51 (d, J = 1.9 Hz, 1H), 8.37-8.33 (m, 3H), 7.99 (dd, J = 8.0, 2.0 Hz, 1H), 7.84-7.80 (m, 2H), 7.76-7.69 (m, 3H), 7.67-7.59 (m, 4H), 7.55-7.48 (m, 5H), 7.28-7.24 (m, 1H), 7.18 (dd, J = 8.3, 0.9 Hz, 1H), 7.10-7.07 (m, 2H), 6.90-6.87 (m, 2H), 4.41-4.35 (m, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 183.4, 182.9, 159.4, 159.0, 150.8, 146.3, 138.9, 137.3, 134.2, 134.0, 133.9, 133.7, 133.6, 131.8 (2C), 131.7, 130.9 (2C), 130.1 (2C), 129.7, 129.2 (2C), 129.1, 129.0, 128.6 (2C), 128.2, 128.1, 128.0, 127.3, 127.2 (2C), 126.2, 125.5, 124.9, 124.7, 124.1, 123.6, 123.09, 123.05, 122.7, 120.8, 115.3 (2C), 114.4 (2C), 66.6, 66.4; HRMS-ESI (m / z): [M + H] + Calculate for C 49 H 33 N2O4, 713.2435; found, 713.2447.

[0041] <Example 5> (Synthesis of the composition of formula (16)) Under an argon atmosphere, a DMF solution (1.0 mL) of phenol (0.10 mmol, 0.0102 g) was added to a DMF suspension (1.0 mL) of sodium hydride (55% in oil, 0.37 mmol, 0.0160 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (1.0 mL) of 2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (31), 0.10 mmol, 0.0587 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, toluene was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by preparative thin-layer chromatography (dichloromethane) to obtain 2-{4-(2-phenoxyethoxy)phenyl}-1,4,5-triphenyl-1H-imidazole (formula (16), 0.0097 g, yield 17%). The reaction formula is shown in formula (38) below.

[0042] [ka]

[0043] The melting point (Mp) of the composition of formula (16), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 186.9-187.4℃; IR (ATR): v max 3065, 2914, 1600, 1496, 1483, 1236, 1188, 1065, 928, 838 cm -1 ; 1H NMR (500 MHz, CDCl3): δ (ppm) 7.60 (d, J = 7.2 Hz, 2H), 7.37-7.34 (m, 2H), 7.29-7.16 (m, 11H), 7.12-7.10 (m, 2H), 7.04-7.01 (m, 2H), 6.97-6.92 (m, 3H), 6.82-6.79 (m, 2H), 4.27 (s, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 158.6, 158.5, 146.8, 138.0, 137.2, 134.5, 131.1 (2C), 130.7, 130.5, 130.3 (2C), 129.5 (2C), 129.0 (2C), 128.4 (2C), 128.3 (2C), 128.14, 128.10 (2C), 127.8, 127.3 (2C), 126.5, 123.5, 121.1, 114.6 (2C), 114.2 (2C), 66.4, 66.3; HRMS-ESI (m / z): [M + H] + Calculate for C 35 H 29 N2O2, 509.2224; found, 509.2228.

[0044] <Example 6> (Synthesis of the composition of formula (20)) Under an argon atmosphere, a DMF solution (3.0 mL) of phenol (0.30 mmol, 0.0286 g) was added to a DMF suspension (3.0 mL) of sodium hydride (55% in oil, 1.0 mmol, 0.0440 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (1.0 mL) of 2-{4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (33), 0.24 mmol, 0.143 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, toluene was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by preparative thin-layer chromatography (dichloromethane) to obtain 2-{4-(2-phenoxyethoxy)phenyl}-1-phenyl-1H-phenanthro[9,10-d]imidazole (formula (20), 0.113 g, yield 91%). The reaction formula is shown in formula (39) below.

[0045] [ka]

[0046] The melting point (Mp) of the composition of formula (20), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 224.0-224.5℃; IR (ATR): v max 3053, 2935, 1609, 1598, 1497, 1453, 1388, 1240, 1180, 1061, 942, 842 cm -1 ; 1H NMR (500 MHz, CDCl3): δ (ppm) 8.87 (dd, J = 8.0, 1.1 Hz, 1H), 8.76 (d, J = 8.3 Hz, 1H), 8.70 (d, J = 8.3 Hz, 1H), 7.75-7.72 (m, 1H), 7.66-7.57 (m, 4H), 7.52-7.47 (m, 5H), 7.31-7.23 (m, 3H), 7.17-7.16 (m, 1H), 6.98-6.92 (m, 3H), 6.86-6.83 (m, 2H), 4.28 (s, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 159.0, 158.5, 150.9, 138.8, 137.3, 130.8 (2C), 130.1 (2C), 129.7, 129.5 (2C), 129.12 (2C), 129.08, 128.2, 127.9, 127.2, 126.2, 125.5, 124.7, 124.0, 123.4, 123.1, 123.0, 122.7, 121.1, 120.7, 114.6 (2C), 114.3 (2C), 66.4, 66.3; HRMS-ESI (m / z): [M + H] + Calculate for C 35 H 27 N2O2, 507.2067; found, 507.2076.

[0047] <Example 7> (Synthesis of the composition of formula (17)) Under an argon atmosphere, a DMF solution (2.0 mL) of 1-naphthol (0.40 mmol, 0.0572 g) was added to a DMF suspension (2.0 mL) of sodium hydride (55% in oil, 0.60 mmol, 0.0264 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (2.0 mL) of 2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (31), 0.20 mmol, 0.117 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, toluene was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by preparative thin layer chromatography (dichloromethane) to obtain 2-[4-{2-(naphthalene-1-yloxy)ethoxy}phenyl]-1,4,5-triphenyl-1H-imidazole (formula (17), 0.0487 g, yield 44%). The reaction formula is shown in formula (40) below.

[0048] [ka]

[0049] The melting point (Mp) of the composition of formula (17), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 201.0-201.6 ℃; IR (ATR): v max 3049, 2932, 1577, 1496, 1482, 1444, 1398, 1271, 1253, 1237, 1187, 1103, 1076, 940, 837 cm -1 ; 1H NMR (500 MHz, CDCl3): δ (ppm) 8.26 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 7.7 Hz, 1H), 7.62-7.59 (m, 2H), 7.49-7.43 (m, 3H), 7.39-7.343 (m, 3H), 7.29-7.17 (m, 9H), 7.13-7.11 (m, 2H), 7.05-7.02 (m, 2H), 6.86-6.83 (m, 3H), 4.46-4.40 (m, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 158.7, 154.3, 146.8, 138.0, 137.2, 134.50, 134.48, 131.1 (2C), 130.7, 130.5, 130.3 (2C), 129.0 (2C), 128.5 (2C), 128.3 (2C), 128.2, 128.1 (2C), 127.8, 127.4 (3C), 126.5, 126.4, 125.7, 125.6, 125.2, 123.5, 122.1, 120.7, 114.3 (2C), 105.0, 66.7, 66.5; HRMS-ESI (m / z): [M + H] + Calculate for C 39 H 31 N2O2, 559.2380; found, 559.2390.

[0050] <Example 8> (Synthesis of the composition of formula (21)) Under an argon atmosphere, a DMF solution (2.0 mL) of 4-phenylphenol (0.20 mmol, 0.0338 g) was added to a DMF suspension (2.0 mL) of sodium hydride (55% in oil, 0.60 mmol, 0.0320 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (2.0 mL) of 2-{4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (31), 0.20 mmol, 0.117 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, toluene was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by preparative thin-layer chromatography (dichloromethane) to obtain 2-[4-{2-([1,1-biphenyl]-4-yloxy)ethoxy}phenyl]-1,4,5-triphenyl-1H-imidazole (formula (21), 0.102 g, yield 86%). The reaction formula is shown in formula (41) below.

[0051] [ka]

[0052] The melting point (Mp) of the composition of formula (21), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 204.6-205.4℃; IR (ATR): v max 3056, 2925, 1609, 1520, 1484, 1452, 1367, 1243, 1181, 1066, 930, 835 cm -1 ; 1H NMR (500 MHz, CDCl3): δ (ppm) 7.61-7.58 (m, 2H), 7.56-7.50 (m, 4H), 7.42-7.35 (m, 4H), 7.31-7.17 (m, 10H), 7.13-7.11 (m, 2H), 7.05-6.98 (m, 4H), 6.83-6.81 (m, 2H), 4.34-4.29 (m, 4H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 158.6, 158.1, 146.8, 140.7, 138.0, 137.2, 134.5, 134.2, 131.1 (2C), 130.7, 130.5, 130.3 (2C), 129.0 (2C), 128.7 (2C), 128.5 (2C), 128.3 (2C), 128.2 (3C), 128.1 (2C), 127.8, 127.4 (2C), 126.7 (3C), 126.5, 123.6, 114.9 (2C), 114.2 (2C), 66.5, 66.4; HRMS-ESI (m / z): [M + H] + Calculate for C 41 H 33 N2O2, 585.2537; found, 585.2550.

[0053] <Example 9> (Synthesis of the composition of formula (24)) Under an argon atmosphere, a DMF solution (10 mL) of 4-{1-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazol-2-yl}phenol (1.0 mmol, 0.389 g) was added to a DMF suspension (10 mL) of potassium carbonate (3.0 mmol, 0.414 g) ground in a mortar. After stirring at room temperature for 1 hour, a DMF solution (10 mL) of 1,2-bis(tosyloxy)ethane (3.0 mmol, 1.11 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with dichloromethane, and the combined organic layers were washed three times with water and once with saturated saline, and dried over anhydrous sodium sulfate. The drying agent was removed by filtration, and the filtrate was evaporated under reduced pressure to obtain a crude product, which was then separated by silica gel column chromatography (dichloromethane / toluene / ethyl acetate=5:5:1) to obtain 2-[4-{1-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazol-2-yl}phenoxy]ethyl p-toluenesulfonate (formula (42), 0.491 g, yield 80%) as a white solid. The reaction formula is shown in formula (43) below. Next, under an argon atmosphere, a DMF solution (3.0 mL) of 4-(benzo[c][1,2,5]thiadiazol-4-yl)phenol (0.30 mmol, 0.0688 g) was added to a DMF suspension (3.0 mL) of sodium hydride (55% in oil, 1.0 mmol, 0.0436 g) washed with hexane. After stirring at room temperature for 1 hour, a DMF solution (3.0 mL) of 2-{4-(1-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenoxy}ethyl p-toluenesulfonate (formula (42), 0.30 mmol, 0.186 g) was added dropwise and stirred at room temperature for 24 hours. Water was added to the reaction mixture to stop the reaction, and the organic layer was separated. The aqueous layer was extracted three times with chloroform, and the combined organic layers were washed three times with water and once with saturated saline, and then dried over anhydrous sodium sulfate. The drying agent was removed by filtration, toluene was added to the filtrate, and the solvent was distilled off under reduced pressure to obtain a crude product, which was separated by silica gel column chromatography (chloroform / ethyl acetate = 20:1) and preparative thin layer chromatography (chloroform / ethyl acetate = 10:1) to obtain 4-{4-(2-[4-{1-(4-methoxyphenyl)-4,5-diphenyl-1H-imidazol-2-yl}phenoxy]ethoxy)phenyl}benzo[c][1,2,5]thiadiazole (formula (24), 0.0459 g, yield 23%). The reaction formula is shown in the following formula (44).

[0054] [ka]

[0055] The melting point (Mp) of the composition of formula (24), the infrared absorption spectrum (ATR method): IR (ATR), 1 H NMR spectrum, 13 The results of C NMR spectrum and accurate mass analysis (electrospray ionization method): HRMS-ESI are shown respectively. Mp 223.8-224.5℃; IR (ATR): v max3060, 2927, 1606, 1511, 1483, 1234, 1176, 1063, 935, 840 cm -1 ; 1 H NMR (500 MHz, CDCl3): δ (ppm) 7.98-7.94 (m, 1H), 7.91-7.89 (m, 2H), 7.68-7.63 (m, 2H), 7.60-7.58 (m, 2H), 7.42-7.38 (m, 2H), 7.26-7.08 (m, 10H), 6.98-6.94 (m, 2H), 6.87-6.84 (m, 2H), 6.78-6.75 (m, 2H), 4.40-4.33 (m, 4H), 3.77 (s, 3H); 13 C NMR (126 MHz, CDCl3): δ (ppm) 159.0, 158.8, 158.5, 155.6, 153.5, 146.9, 137.9, 134.6, 134.0, 131.1 (2C), 130.9, 130.7, 130.5 (2C), 130.30 (2C), 130.27, 130.0, 129.7, 129.5 (2C), 128.3 (2C), 128.1 (2C), 127.8, 127.3 (2C), 127.0, 126.4, 123.7, 119.9, 114.8 (2C), 114.3 (2C), 114.2 (2C), 66.6, 66.4, 55.3; HRMS-ESI (m / z): [M + H] + calcd for C 42 H 33 N4O3S, 673.2268; found, 673.2266.

Claims

1. A composition represented by the following formula (1): [Formula 1] (In formula (1), E 1 is represented by the following formula (2) or (3), E 2 is expressed by the following formula (4) or (5). [Case 2] [C3] In formulas (2) to (5), R 1 ~R 2 , R 4 ~R 15 , R 17 ~R 32 are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. 3 and R 16 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an aralkyloxy group, an aryloxy group, an amino group, an amido group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a formyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

2. In the formula (1), E 1 The composition according to claim 1 , wherein the compound is represented by the following formula (6), (7), or (23): [C4] (In formulas (6), (7), and (23), Ph is a phenyl group.)

3. In the formula (1), E 2 The composition according to claim 1, wherein the compound is represented by any one of the following formulas (8) to (12): [C5]

4. An organic fluorescent material comprising the composition according to any one of claims 1 to 3.

5. 5. The organic fluorescent material of claim 4, which is a fluorescent patterning material, a fluorescent switching material or a fluorescent sensor material.

6. A step of reacting a compound represented by the following formula (2′) or (3′) with a compound represented by the following formula (13) to prepare a compound represented by the following formula (2″) or (3″); A step of reacting a compound represented by the formula (2″) or (3″) with a compound represented by the following formula (4′) or (5′) to prepare a composition represented by the formula (1); A method for producing the composition according to any one of claims 1 to 3, comprising: [C6] [C7] [C8] [C9] (In the formula (13), (2″) or (3″), X 1 and X 2 are each, independently of one another, a leaving group used in a nucleophilic substitution reaction.

7. A step of dissolving the composition according to any one of claims 1 to 3 in an organic solvent to prepare a solution of the composition; A step of adding a solution of the composition to a poor solvent for the composition, stirring the solution, and then filtering the solution through a filter; recovering the film of composition deposited on the filter after said filtration; The method for producing a thin film comprising the steps of:

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