A carborane derivative, a preparation method and application thereof

Abstract

This invention discloses a carborane derivative, its preparation method, and its applications. Specifically, it involves the reaction of carborane with indole or pyrrole derivatives to prepare carborane-indole / pyrrole quinoxaline compounds. This invention combines a carborane derivative with a 3D structure with a nitrogen-containing heterocyclic quinoxaline with a special 2D electronic structure to obtain compounds with a 3D+2D structure. The synthesis method is simple, mild, and efficient. These compounds avoid aggregation-induced fluorescence quenching caused by 2D structure π-π stacking in the aggregated state, exhibiting good aggregation-induced emission effect. They also have good optical effects, displaying full-color light under 365nm ultraviolet light, and have applications in organic light-emitting materials.

Description

Technical Field

[0001] This invention belongs to the field of organic light-emitting materials technology, specifically relating to a carborane derivative, its preparation method, and its application. Background Technology

[0002] Aggregation-induced emission (AIE) materials have advantages such as high luminescence efficiency, high sensitivity, and good stability in the aggregated state. In recent years, they have been widely used in environmental monitoring, food quality control, health diagnosis, biochemical sensors with bioimaging functions, optoelectronic devices, and optical diagnostic reagents.

[0003] Indole / pyrroloquinoxaline possesses excellent fluorescence and photophysical properties, and is often used as a core structural unit in organic light-emitting materials (OLEDs) for important applications such as fluorescent probes and chemical sensing detection (Photochem. Photobiol. A. 2022, 431, 114046). However, the large planar rigid conjugated system formed by multiple aromatic rings of indole / pyrrolo[1,2-a]quinoxaline often suffers from aggregation-induced quenching (ACQ) due to the π-π stacking of its two-dimensional (2D) structure in the aggregated state, which limits its application in OLED technology to some extent. Scientists have introduced aromatic ring molecular rotors to improve the ACQ problem of this type of material. However, since the aromatic ring molecular rotor is still a two-dimensional aromatic structure, its application in AIE materials is limited. How to develop new molecular rotor systems with better performance remains a bottleneck in the development of AIE materials.

[0004] To address the aforementioned issues, dicarboborane (carborane), possessing a three-dimensional (3D) aromatic stereostructure, was introduced into the indole / pyrrolo[1,2-a]quinoxaline structure. Due to the 3D stereostructure of carborane, close molecular packing is effectively prevented. Compounds containing carborane molecules exhibit multiple emission, thermally activated delayed fluorescence (TADF), aggregation-induced emission (AIE), ultralong organic phosphorescence, mechanochromism, and thermochromism, providing a universal unit for preparing multifunctional optical materials. Therefore, introducing the nitrogen heterocyclic structure of indole / pyrroloquinoxaline, with its excellent photophysical properties, into the carborane structure, which has significant advantages in AIE applications, may yield indole / pyrroloquinoxaline-like carborane compounds with aggregation-induced emission (AIE) effects, overcoming the ACQ problem of phenylindole / pyrroloquinoxaline and further expanding the application of indole / pyrroloquinoxaline in organic light-emitting materials. How to efficiently prepare carborane indole / pyrrolo[1,2-a]quinoxaline compounds is also an urgent problem to be solved. Summary of the Invention

[0005] To address the aforementioned issues, this invention provides a carborane derivative by linking a 3D carborane derivative with a nitrogen-containing heterocyclic quinoxaline having a unique 2D electronic structure, thereby obtaining a compound with a good AIE effect. This further expands the range of compounds in the field of organic light-emitting materials. Moreover, the synthesis method is simple and efficient, with a mild reaction temperature and high atom utilization.

[0006] The present invention also provides a method for preparing the above-mentioned carborane derivatives and their application in organic light-emitting materials.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows:

[0008] A carborane derivative, wherein the carborane derivative is a compound represented by Formula I.

[0009]

[0010] Among them, ring A is an aromatic ring or does not exist;

[0011] R 1 Independently selected from H, C 1-3 Any one of alkyl or phenyl groups;

[0012] R 2 Substituents at any position on the aromatic ring, independently selected from H, C 1-3 Any one of alkyl groups and halogens;

[0013] R 3 Independently selected from H, C 1-3 Any one of the alkyl groups;

[0014] R 4 Substituents at any position on the aromatic ring, independently selected from H, C 1-3 Any one of alkyl groups or halogens.

[0015] It should be noted that the carborane in Formula I is a cage-like molecule composed of two carbon-hydrogen vertices and ten boron-hydrogen vertices.

[0016] As a further improvement, when ring A is present and is an aromatic ring, the R... 1 R 2 For H;

[0017] The R 3 Independently selected from H, C 1-3 Any one of the alkyl groups;

[0018] The R 4 Substituents at any position on the aromatic ring, independently selected from H, C 1-3 Any one of alkyl, -F, -Cl, and -Br.

[0019] When ring A does not exist, the R 1 Independently selected from H, C 1-3 Any one of alkyl or phenyl groups;

[0020] The R 2 It can be a substituent at any position on the aromatic ring, independently selected from H, -CH3, -F, and -Cl;

[0021] The R 3 Selected from H; the R 4 It does not exist.

[0022] As a further improvement, the carborane derivative includes any one of the following compounds:

[0023]

[0024]

[0025] The carborane derivatives disclosed in this invention combine a carborane derivative with a 3D stereostructure with a 2D planar nitrogen-containing heterocyclic quinoxaline with a special electronic structure to obtain a carborane indole / pyrroloquinoxaline derivative with a 3D+2D structure. This type of compound avoids aggregation-induced fluorescence quenching caused by π-π stacking in the 2D planar state in the aggregated state, and has a better aggregation-induced emission effect. At the same time, it has better other optical effects and can display full-color light under 365nm ultraviolet light. It can be used as an organic light-emitting material for anti-counterfeiting and information encryption applications.

[0026] The method for preparing the carborane derivatives described above includes:

[0027] The aldehyde-based o-carborane derivative of Formula II, the compound of Formula III, and Lewis acid were reacted in a solvent at 30–80 °C for 1.5–4 h, and then reacted with triethylamine and an oxidant for 2–60 min to obtain the compound of Formula I.

[0028]

[0029] The present invention combines a carborane derivative with a stereostructure with a planar nitrogen-containing heterocyclic quinoxaline with a special electronic structure to obtain a carborane indole / pyrroloquinoxaline derivative. This type of compound avoids aggregation-induced fluorescence quenching caused by π-π stacking in the planar state in the aggregated state, and has a better aggregation-induced emission effect. At the same time, it has good other optical effects and can display full-color light under 365nm ultraviolet light. It can be used as an organic light-emitting material for anti-counterfeiting and information encryption applications. The preparation method of the present invention is simple to operate, highly efficient, mild in reaction temperature, and has broad substrate versatility.

[0030] Preferably, the Lewis acid includes any one of boron trifluoride diethyl ether, metal halide, p-toluenesulfonic acid, phosphoric acid, magnesium sulfate, trifluoroacetic acid, etc. Therefore, the compound of formula II can react better with the compound of formula III.

[0031] Preferably, the solvent includes any one of acetonitrile, toluene, chloroalkanes, etc., and the amount added is such that the mass ratio of the aldehyde-based o-carborane derivative to the solvent is 1:(17-60). Under this type of solvent and reaction concentration, the reactants can react completely.

[0032] Furthermore, the oxidant can be any one of potassium permanganate, [bis(trifluoroacetoxy)iodo]benzene, 2,3-dichloro-5,6-dicyanobenzoquinone, iodophenyldiacetic acid, etc. This can achieve a better oxidation effect.

[0033] Preferably, the molar ratio of the aldehyde-based ortho-carborane derivative, the compound of formula III, the Lewis acid, the triethylamine, and the oxidant is 1:(0.8-1.2):(0.05-0.2):(0.1-0.3):(1-1.5).

[0034] Furthermore, the metal halide is selected from one of tin dichloride or its hydrate, aluminum trichloride, zinc chloride, etc.

[0035] Furthermore, the chloroalkane is selected from one of dichloromethane, trichloromethane, dichloroethane, etc.

[0036] This invention provides the application of the carborane derivatives mentioned above in organic light-emitting materials, especially in the fields of organic light-emitting diodes, LED displays, anti-counterfeiting materials, and information encryption.

[0037] Compared with the prior art, the present invention has the following beneficial effects:

[0038] The carborane derivatives disclosed in this invention combine carborane derivatives with stereostructures with planar nitrogen-containing heterocyclic quinoxalines with special electronic structures to obtain carborane indole / pyrroloquinoxaline derivatives. These compounds, in their aggregated state, avoid aggregation-induced fluorescence quenching caused by π-π stacking in the planar state, exhibiting better aggregation-induced emission effects. They also possess other good optical effects, displaying full-color light under 365nm ultraviolet light, making them suitable as organic light-emitting materials for anti-counterfeiting and information encryption applications. Furthermore, the preparation method of this invention is simple to operate, highly efficient, has a mild reaction temperature, and broad substrate applicability. Attached Figure Description

[0039] Figure 1 This is the hydrogen NMR spectrum from Example 1;

[0040] Figure 2 This is the carbon NMR spectrum from Example 1;

[0041] Figure 3 This is the boron NMR spectrum from Example 1;

[0042] Figure 4 This is the hydrogen NMR spectrum from Example 10;

[0043] Figure 5 This is the carbon NMR spectrum from Example 10;

[0044] Figure 6 This is the boron NMR spectrum from Example 10;

[0045] Figure 7 These are solid-state luminescence images of the compounds in Examples 1-14 under sunlight and 365nm ultraviolet light;

[0046] Figure 8 These are the fluorescence emission spectra of Example 4 in different solutions;

[0047] Figure 9 These are the fluorescence emission spectra of Example 11 in different solutions;

[0048] Figure 10 These are the emission patterns of Examples 1-3 and Examples 5-7 under 365nm ultraviolet light at a water content of 0%-80%;

[0049] Figure 11 The images show the emission patterns of Examples 8-10 and 12 under 365nm ultraviolet light at a water content of 0%-80%, and the emission patterns of Examples 13-14 under 365nm ultraviolet light at a water content of 0%-90%.

[0050] Figure 12 The fluorescence emission spectra of Comparative Example 2 in different solutions;

[0051] Figure 13 This is the emission diagram of Comparative Example 2 under 365nm ultraviolet light in different solutions;

[0052] Figure 14 Images of the compounds from Examples 7, 9, and 11-14 coated on filter paper strips under sunlight and 365nm ultraviolet light;

[0053] Figure 15 The luminescence patterns of the compounds from Examples 1-6, 8, and 10 coated on filter paper strips under sunlight and 365nm ultraviolet light. Detailed Implementation

[0054] This invention provides a carborane derivative, wherein the carborane derivative is a compound represented by Formula I;

[0055]

[0056] Among them, ring A may or may not exist;

[0057] R 1 Independently selected from H, C 1-3 Any one of alkyl and aryl groups;

[0058] R 2 Substituents at any position on the aromatic ring, independently selected from H, C 1-3 Any one of alkyl groups and halogens;

[0059] R 3 Independently selected from H, C 1-3 Any one of the alkyl groups;

[0060] R 4 Substituents at any position on the aromatic ring, independently selected from H, C 1-3 Any one of alkyl groups and halogens;

[0061] This invention also provides a method for preparing carborane derivatives:

[0062] The aldehyde-based o-carborane derivative of Formula II, the compound of Formula III, and Lewis acid were reacted in a solvent at 30–80 °C for 1.5–4 h, and then reacted with triethylamine and an oxidant for 2–60 min to obtain the compound of Formula I.

[0063]

[0064] The present invention also provides the application of the carborane derivatives described above in organic light-emitting materials.

[0065] The present invention will be further described below with reference to specific embodiments.

[0066] I. Examples of Carborane Derivatives and Their Preparation Methods

[0067] Example 1

[0068] The carborane derivative of this embodiment has the following structural formula:

[0069]

[0070]

[0071] Its preparation method includes the following steps:

[0072] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.17 g (0.8 mmol) of 2-(1H-indol-1-yl)aniline (commonly available product, CAS: 473918-48-8), and 7.8 g of acetonitrile were added to a reaction flask. 7 mg (0.05 mmol) of zinc chloride was added with stirring, and the mixture was stirred at 30 °C for 4 h. 10 mg (0.1 mmol) of triethylamine was added with stirring, followed by 0.16 g (1 mmol) of potassium permanganate. The mixture was stirred for 60 min, and the reaction solution was filtered. The filter cake was washed with chloroform and dried to give 0.26 g of a yellow solid, yield 71%, melting point 269-271 °C.

[0073] The 1H NMR spectrum of the product prepared in Example 1 is shown below. Figure 1 As shown, 1 H NMR (400MHz, CDCl3): δ8.51(dd,J=8.4,0.8Hz,1H),8.46(d,J=8.3Hz,1H),8.03(d,J=8.0Hz,1H),7.90(dd,J=8.0,1.5Hz,1H),7.7 4(s,1H),7.67(ddd,J=8.6,7.4,1.6Hz,1H),7.60(ddd,J=8.6,7.0,1.2Hz,1H),7.52-7.47(m,1H),7.47-7.42(m,1H),5.59(s,1H).

[0074] The carbon NMR spectrum of the product prepared in Example 1 is shown below. Figure 2 As shown, 13 C{ 1 H}NMR (101MHz, CDCl3): δ146.27,133.84,132.67,130.46,129.98,128.96,12 5.57,125.52,124.37,123.40,123.33,114.70,114.40,104.84,74.18,58.72.

[0075] The NMR boron spectrum of the product prepared in Example 1 is shown below. Figure 3 As shown, 11 B{ 1 H}NMR(128MHz, CDCl3): δ-2.80(2B),-8.70(4B),-12.10(2B),-13.39(2B).

[0076] Mass spectrometry data (HRMS(ESI)) m / z of the product prepared in Example 1: [M+Cl] - C 17 H 20 B 10 ClN2- 397.2246; Actual value 397.2257.

[0077] Example 2

[0078] The carborane derivative of this embodiment has the following structural formula:

[0079]

[0080]

[0081] Its preparation method includes the following steps:

[0082] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.24 g (1.1 mmol) of 2-(5-methyl-1H-indol-1-yl)aniline (CAS: 1245500-24-6, detailed preparation process can be found in the literature Journal of Organic Chemistry, 2017, 82, 10158), and 10 g of chloroform were added to a reaction flask. 12 mg (0.1 mmol) of 85% phosphoric acid was added with stirring, and the reaction was stirred at 40 °C for 3 h. 20 mg (0.2 mmol) of triethylamine was added with stirring, followed by 0.52 g (1.2 mmol) of [bis(trifluoroacetoxy)iodide]benzene. The reaction was stirred for 40 min. The reaction solution was filtered, the filter cake was washed with chloroform, and dried to obtain 0.29 g of yellow solid, yield 78%, melting point 292-294 °C.

[0083] The 1H NMR spectrum data of the product prepared in Example 2 1 H NMR (400MHz, CDCl3): δ8.48 (dd, J=8.5, 0.9Hz, 1H), 8.33 (d, J=8.9Hz, 1H), 7.89 (dd, J=8.0 ,1.5Hz,1H),7.78(s,1H),7.71-7.60(m,2H),7.48-7.37(m,2H),5.59(s,1H),2.58(s,3H).

[0084] The carbon NMR spectrum data of the product prepared in Example 2, 13 C{ 1 H}NMR (101MHz, CDCl3): δ146.09,133.78,133.04,131.13,130.42,130.37,129.86,12 9.35,127.56,125.65,124.15,122.53,114.58,114.03,104.26,74.25,58.71,21.44.

[0085] The NMR boron spectrum data of the product prepared in Example 2, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.89(2B),-8.78(4B),-12.07(2B),-13.37(2B).

[0086] Mass spectrometry data (HRMS (ESI)) m / z) of the product prepared in Example 2: Theoretical value [M] + C 18 H 22 B 10 N2 + 376.2713; Actual value 376.2708.

[0087] Using this embodiment, R in Formula II can be prepared accordingly. 4 For the corresponding compounds of ethyl, propyl, and isopropyl, based on C 1-3 The properties of alkyl groups are similar, and the specific preparation and application effects should be comparable to those in this embodiment.

[0088] Example 3

[0089] The carborane derivative of this embodiment has the following structural formula:

[0090]

[0091]

[0092] Its preparation method includes the following steps:

[0093] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.27 g (1.2 mmol) of 2-(3-methyl-1H-indol-1-yl)aniline (CAS: 870072-59-6, detailed preparation process can be found in J.Org.Chem., 2024, 89, 5, 3573), and 6.6 g of dichloromethane were added to a reaction flask. 27 mg (0.12 mmol) of tin dichloride dihydrate was added under stirring, and the reaction was stirred at 50 °C for 2 h. 25 mg (0.25 mmol) of triethylamine was added under stirring, followed by 0.39 g (1.2 mmol) of iodophenyldiacetic acid. The reaction was stirred for 20 min. The reaction solution was filtered, the filter cake was washed with chloroform, and dried to obtain 0.11 g of orange solid, yield 30%, melting point 252-254 °C.

[0094] The 1H NMR spectrum data of the product prepared in Example 3 1H NMR (400MHz, CDCl3): δ8.42(dd,J=10.8,8.9Hz,2H),7.99(d,J=8.1Hz,1H),7.81(dd,J=7.9,1.4 Hz, 1H), 7.64-7.56 (m, 2H), 7.50 (t, J = 7.5Hz, 1H), 7.40-7.34 (m, 1H), 5.72 (s, 1H), 3.04 (s, 3H).

[0095] The carbon NMR spectrum data of the product prepared in Example 3, 13 C{ 1 H}NMR (101MHz, CDCl3): δ147.06,132.38,132.11,131.19,130.57,130.10,129.67,12 5.80,123.84,123.54,122.87,121.34,114.36,114.23,111.53,77.21,63.63,15.04.

[0096] The NMR boron spectrum data of the product prepared in Example 3, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.88(1B),-3.91(1B),-7.66(1B),-8.84(2B),-11.18(2B),-12.69(2B),-14.05(1B).

[0097] Mass spectrometry data (HRMS (ESI)) m / z) of the product prepared in Example 3: Theoretical value [MH] - C 18 H 21 B 10 N2 - 375.2635; Actual value 375.2643.

[0098] Using this embodiment, R in Formula II can be prepared accordingly. 3 For the corresponding compounds of ethyl, propyl, and isopropyl, based on C 1-3 The properties of alkyl groups are similar, and the specific preparation and application effects should be comparable to those in this embodiment.

[0099] Example 4

[0100] The carborane derivative of this embodiment has the following structural formula:

[0101]

[0102]

[0103] Its preparation method includes the following steps:

[0104] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.23 g (1 mmol) of 2-(6-fluoro-1H-indol-1-yl)aniline (CAS: 1355020-10-8, detailed preparation process can be found in the literature Chem. Commun., 2021, 57, 11980), and 7.4 g of chloroform were added to the reaction flask. 13 mg (0.1 mmol) of aluminum trichloride was added under stirring, and the reaction was stirred at 50 °C for 2 h. 20 mg (0.2 mmol) of triethylamine was added and stirred, followed by 0.39 g (1.2 mmol) of iodophenyldiacetic acid, and the reaction was stirred for 10 min. The reaction solution was filtered, the filter cake was washed with chloroform, and dried to obtain 0.30 g of yellow solid, yield 78%, melting point 283-285 °C.

[0105] The 1H NMR spectrum data of the product prepared in Example 4 1 H NMR (400MHz, CDCl3): δ8.35 (dd, J=8.4, 0.8Hz, 1H), 8.14 (dd, J=10.6, 2.0Hz, 1H), 7.98 (dd, J=8.9, 5.7Hz, 1H) ,7.90(dd,J=8.0,1.5Hz,1H),7.74-7.65(m,2H),7.50-7.44(m,1H),7.30(td,J=8.9,2.1Hz,1H),5.57(s,1H).

[0106] The carbon NMR spectrum data of the product prepared in Example 4, 13 C{ 1 H}NMR (101MHz, CDCl3): δ162.44, 146.27, 133.82, 132.11 (d, J = 12.1Hz), 130.56, 130.03 (d, J = 5.9Hz), 126.20 (d, J =3.8Hz),125.43,124.85-124.40(m),114.36,113.25,112.99,104.90(d,J=1.6Hz),100.98,100.70,73.99,58.65.

[0107] The NMR boron spectrum data of the product prepared in Example 4, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.80(2B),-8.72(4B),-12.16(2B),-13.36(2B).

[0108] Mass spectrometry data (HRMS(ESI) m / z) of the product prepared in Example 4: Theoretical value [M+COOH] -C 18 H 20 B 10 FN2O2 - 425.2439; Actual value 425.2443.

[0109] Example 5

[0110] The carborane derivative of this embodiment has the following structural formula:

[0111]

[0112]

[0113] Its preparation method includes the following steps:

[0114] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.24 g (1 mmol) of 2-(5-chloro-1H-indol-1-yl)aniline (CAS: 2130819-28-0, for detailed preparation process see literature J.Org.Chem., 2024, 89, 3573), and 5 g of dichloroethane were added to a reaction flask. 18 mg (0.15 mmol) of magnesium sulfate was added under stirring, and the reaction was stirred at 60 °C for 1.5 h. 30 mg (0.3 mmol) of triethylamine was added and stirred, followed by 0.3 g (1.3 mmol) of 2,3-dichloro-5,6-dicyanobenzoquinone. The reaction was stirred for 10 min. The reaction solution was filtered, and the filter cake was washed with chloroform and dried to give 0.23 g of a yellow solid, yield 58%, melting point 296-300 °C.

[0115] The 1H NMR spectrum data of the product prepared in Example 5 1 H NMR (400MHz, CDCl3): δ8.41(dd,J=21.0,8.8Hz,2H),7.98(d,J=1.8Hz,1H),7.92(d,J=8.0H z,1H),7.73-7.64(m,2H),7.53(dd,J=9.2,2.0Hz,1H),7.47(t,J=7.7Hz,1H),5.56(s,1H).

[0116] The carbon NMR spectrum data of the product prepared in Example 5, 13 C{ 1 H}NMR (101MHz, CDCl3): δ146.03,133.78,130.88,130.70,130.32,130.02,129.90 ,129.12,126.50,125.87,124.81,122.36,115.51,114.54,103.98,73.93,58.66.

[0117] The NMR boron spectrum data of the product prepared in Example 5, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.24(1B),-3.13(1B),-8.15(1B),-9.24(2B),-12.70(5B).

[0118] Mass spectrometry data (HRMS(ESI) m / z) of the product prepared in Example 5: Theoretical value [M+COOH] - C 18 H 20 B 10 ClN2O2 - 441.2144; Actual value 441.2153.

[0119] Example 6

[0120] The carborane derivative of this embodiment has the following structural formula:

[0121]

[0122]

[0123] Its preparation method includes the following steps:

[0124] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.29 g (1 mmol) of 2-(5-bromo-1H-indol-1-yl)aniline (CAS: 1264954-12-2, detailed preparation process can be found in the literature Org. Lett., 2014, 16, 6112), and 2.9 g of toluene were added to the reaction flask. 23 mg (0.2 mmol) of trifluoroacetic acid was added with stirring, and the reaction was stirred at 50 °C for 3.5 h. 20 mg (0.2 mmol) of triethylamine was added with stirring, followed by 0.48 g (1.5 mmol) of iodophenyldiacetic acid. The reaction was stirred for 10 min. The reaction solution was filtered, the filter cake was washed with chloroform, and dried to give 0.35 g of yellow solid, yield 80%, melting point 314-316 °C.

[0125] The 1H NMR spectrum data of the product prepared in Example 6 1 H NMR (400MHz, CDCl3): δ8.43 (dd, J=8.5, 0.8Hz, 1H), 8.33 (d, J=9.2Hz, 1H), 8.16 (d, J=1.9 Hz, 1H), 7.92 (dd, J = 8.0, 1.5Hz, 1H), 7.72-7.63 (m, 3H), 7.51-7.45 (m, 1H), 5.56 (s, 1H).

[0126] The carbon NMR spectrum data of the product prepared in Example 6 13 C{ 1 H}NMR (101MHz, CDCl3): δ146.06,133.80,131.15,130.71,130.44,130.32,130.01 ,128.36,126.33,125.62,124.83,116.78,115.78,114.60,103.86,73.93,58.67.

[0127] The NMR boron spectrum data of the product prepared in Example 6, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.22(1B),-3.02(1B),-8.12(1B),-9.25(2B),-11.39(2B),-12.84(2B),-14.07(1B).

[0128] Mass spectrometry data (HRMS(ESI) m / z) of the product prepared in Example 6: Theoretical value [M+K] + C 17 H 19 B 10 BrN2K + 479.1299; Actual value 479.1276.

[0129] Example 7

[0130] The carborane derivative of this embodiment has the following structural formula:

[0131]

[0132] Its preparation method includes the following steps:

[0133] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.16 g (1 mmol) of 2-(1H-pyrrolo-1-yl)aniline, and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of p-toluenesulfonic acid was added with stirring, and the mixture was stirred at 65 °C for 3 h. 20 mg (0.2 mmol) of triethylamine was added with stirring, followed by 0.39 g (1.2 mmol) of iodophenyldiacetic acid. The mixture was stirred for 10 min, and the reaction solution was filtered. The filter cake was washed with chloroform and dried to give 0.29 g of a white solid, with a yield of 92% and a melting point of 295-297 °C.

[0134] The 1H NMR spectrum data of the product prepared in Example 7 1H NMR (400MHz, CDCl3): δ8.02 (dd, J=2.7, 1.1Hz, 1H), 7.85 (dd, J=8.1, 1.6Hz, 2H), 7.60-7.54 (m, 1H), 7.49-7.43 (m, 1H), 7.39 (dd, J=4.3, 1.1Hz, 1H), 6.95 (dd, J=4.3, 2.8Hz, 1H), 5.56 (s, 1H).

[0135] The carbon NMR spectrum data of the product prepared in Example 7, 13 C{ 1 H}NMR (101MHz, CDCl3): δ144.75,133.94,130.09,129.06,127.25,125.64,122.47,115.42,114.68,113.71,111.12,74.19,58.29.

[0136] The NMR boron spectrum data of the product prepared in Example 7, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.93(2B),-8.81(2B),-9.88(2B),-12.05(2B),-13.55(2B).

[0137] Mass spectrometry data (HRMS(ESI) m / z) of the product prepared in Example 7: Theoretical value [M+Na] + C 13 H 18 B 10 N2Na + 335.2298; Actual value 335.2271.

[0138] Example 8

[0139] The carborane derivative of this embodiment has the following structural formula:

[0140]

[0141] Its preparation method includes the following steps:

[0142] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.17 g (1 mmol) of 4-methyl-2-(1H-pyrrolo-1-yl)aniline (CAS: 1224954-97-5, see literature.Org.Chem., 2021, 86, 7390) and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of boron trifluoride ether was added under stirring. The mixture was stirred at 75 °C for 2.5 h. 20 mg (0.2 mmol) of triethylamine was added and stirred. Then 0.39 g (1.2 mmol) of iodophenyl diacetic acid was added and stirred for 10 min. The reaction solution was filtered, the filter cake was washed with chloroform and dried to give 0.29 g of white solid, yield 90%, melting point 292-294 °C.

[0143] The 1H NMR spectrum data of the product prepared in Example 8 1 H NMR (400MHz, CDCl3): δ7.97(d,J=1.7Hz,1H),7.72(d,J=8.2Hz,1H),7.64(s,1H),7.35(dd,J= 4.2, 0.8Hz, 1H), 7.28 (d, J = 1.1Hz, 1H), 6.93 (dd, J = 4.2, 2.8Hz, 1H), 5.55 (s, 1H), 2.56 (s, 3H).

[0144] The carbon NMR spectrum data of the product prepared in Example 8, 13 C{ 1 H}NMR (101MHz, CDCl3): δ143.66,139.87,131.95,129.76,126.99,122.50,115.04,114.52,113.69,110.66,74.31,58.26,21.98.

[0145] The NMR boron spectrum data of the product prepared in Example 8, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.43(1B),-3.55(1B),-8.28(1B),-9.42(2B),-11.44(2B),-12.87(2B),-14.21(1B).

[0146] Mass spectrometry data of the product prepared in Example 8: HRMS (ESI) m / z: theoretical value [MH] - C 14 H 19 B 10 N2 - 325.2479; actual value 325.2462.

[0147] Example 9

[0148] The carborane derivative of this embodiment has the following structural formula:

[0149]

[0150] Its preparation method includes the following steps:

[0151] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.17 g (1 mmol) of 5-methyl-2-(1H-pyrrolo-1-yl)aniline, and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of boron trifluoride ether was added while stirring. The mixture was stirred at 80 °C for 1.5 h. 20 mg (0.2 mmol) of triethylamine was added and stirred. Then 0.39 g (1.2 mmol) of iodophenyldiacetic acid was added and stirred for 5 min. The reaction mixture was filtered, and the filter cake was washed with chloroform and dried to give 0.30 g of white solid, with a yield of 94% and a melting point of 285-287 °C.

[0152] The 1H NMR spectrum data of the product prepared in Example 9 1 H NMR (400MHz, CDCl3): δ7.97 (dd, J=2.7, 1.1Hz, 1H), 7.74 (d, J=8.4Hz, 1H), 7.66 (d, J= 0.7Hz, 1H), 7.40-7.33 (m, 2H), 6.92 (dd, J = 4.3, 2.7Hz, 1H), 5.55 (s, 1H), 2.49 (s, 3H).

[0153] The carbon NMR spectrum data of the product prepared in Example 9, 13 C{ 1 H}NMR (101MHz, CDCl3): δ144.65,135.60,133.93,130.22,129.81,125.15,122.41,115.17,114.40,113.42,110.81,74.32,58.31,20.95.

[0154] The NMR boron spectrum data of the product prepared in Example 9, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-3.04(2B),-8.87(4B),-12.17(2B),-13.56(2B).

[0155] Mass spectrometry data (HRMS (ESI)) m / z) of the product prepared in Example 9: Theoretical value [MH] - C 14 H 19 B 10 N2- 325.2478; Actual value 325.2484.

[0156] Example 10

[0157] The carborane derivative of this embodiment has the following structural formula:

[0158]

[0159] Its preparation method includes the following steps:

[0160] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.17 g (1 mmol) of 2-methyl-6-(1H-pyrrolo-1-yl)aniline (CAS: 1208660-92-7, for detailed preparation process see literature J.Org.Chem.2010,75,3371), and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of boron trifluoride ether was added under stirring. The reaction was stirred at 65 °C for 3 h. After the reaction solution cooled to the reaction temperature, 20 mg (0.2 mmol) of triethylamine was added and stirred. Then, 0.39 g (1.2 mmol) of iodophenyl diacetic acid was added and stirred for 2 min. The reaction solution was filtered, and the filter cake was washed with chloroform and dried to give 0.27 g of yellow solid, yield 83%, melting point 267-269 °C.

[0161] The 1H NMR spectrum data of the product prepared in Example 10 are as follows: Figure 4 As shown, 1 H NMR (400MHz, CDCl3): δ8.50(d,J=8.4Hz,1H),8.23(s,1H),7.88(dd,J=12.8,4.9Hz,2H) ,7.70-7.62(m,2H),7.45-7.40(m,1H),7.33(d,J=8.2Hz,1H),5.59(s,1H),2.67(s,3H).

[0162] The NMR spectral data of the product prepared in Example 10 are as follows: Figure 5 As shown, 13 C{ 1 H}NMR (101MHz, CDCl3): δ146.24,135.9,133.90,133.13,130.48,130.31,129.74,12 6.93,125.47,125.23,124.23,122.91,114.73,114.04,104.81,74.21,58.68,22.73.

[0163] The NMR boron spectrum data of the product prepared in Example 10 are as follows: Figure 6 As shown,11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.36(1B),-3.49(1B),-8.22(1B),-9.36(2B),-11.45(2B),-12.84(2B),-14.21(1B).

[0164] Mass spectrometry data (HRMS (ESI)) m / z) of the product prepared in Example 10: Theoretical value [M] + C 14 H 20 B 10 N2 + 326.2557; Actual value 326.2556.

[0165] Example 11

[0166] The carborane derivative of this embodiment has the following structural formula:

[0167]

[0168]

[0169] Its preparation method includes the following steps:

[0170] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.18 g (1 mmol) of 5-fluoro-2-(1H-pyrrolo-1-yl)aniline, and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of boron trifluoride ether was added with stirring. The mixture was stirred at 65 °C for 3 h. 20 mg (0.2 mmol) of triethylamine was added with stirring, followed by 0.39 g (1.2 mmol) of iodophenyldiacetic acid. The mixture was stirred for 10 min. The reaction solution was filtered, and the filter cake was washed with chloroform and dried to give 0.30 g of a yellow solid with a yield of 92% and a melting point of 290-292 °C.

[0171] The 1H NMR spectrum data of the product prepared in Example 11, 1 H NMR (400MHz, CDCl3): δ7.99 (dd, J=2.7, 1.1Hz, 1H), 7.83 (dd, J=9.1, 4.9Hz, 1H), 7.54 (dd, J=9.0, 2.8Hz, 1H ), 7.41 (dd, J=4.3, 1.1Hz, 1H), 7.31 (ddd, J=9.1, 7.8, 2.8Hz, 1H), 6.95 (dd, J=4.3, 2.7Hz, 1H), 5.50 (s, 1H).

[0172] The carbon NMR spectrum data of the product prepared in Example 11, 13 C{1 H}NMR (101MHz, CDCl3): δ161.19, 158.74, 146.09, 135.07 (d, J = 11.8Hz), 123.94, 122.3 7,117.04,116.80,115.71,115.38,115.00(dd,J=18.3,9.1Hz),111.65,73.95,58.32.

[0173] The NMR boron spectrum data of the product prepared in Example 11, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.88(2B),-8.73(2B),-10.05(2B),-12.13(2B),-13.57(2B).

[0174] Mass spectrometry data (HRMS (ESI)) m / z of the product prepared in Example 11: Theoretical value [M+CH3COOH] - C 15 H 21 B 10 FN2O2 - 390.2518; Actual value 390.2539.

[0175] Example 12

[0176] The carborane derivative of this embodiment has the following structural formula:

[0177]

[0178] Its preparation method includes the following steps:

[0179] 0.17 g (1 mmol) of 1-aldehyde o-carborane, 0.23 g (1 mmol) of 4,5-dichloro-2-(1H-pyrrolo-1-yl)aniline (CAS: 59194-31-9, for detailed preparation process see J. Med. Chem., 1999, 42, 4362), and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of boron trifluoride ether was added under stirring, and the reaction was stirred at 65 °C for 3 h. 20 mg (0.2 mmol) of triethylamine was added and stirred, followed by 0.39 g (1.2 mmol) of iodophenyl diacetic acid. The reaction was stirred for 10 min. The reaction solution was filtered, the filter cake was washed with chloroform, and dried to give 0.32 g of a yellow solid, yield 84%, melting point 309-311 °C.

[0180] The 1H NMR spectrum data of the product prepared in Example 12 1H NMR (400MHz, CDCl3): δ7.99-7.92 (m, 3H), 7.43 (d, J = 4.2Hz, 1H), 7.02-6.96 (m, 1H), 5.44 (s, 1H).

[0181] The carbon NMR spectrum data of the product prepared in Example 12, 13 C{ 1 H}NMR (101MHz, CDCl3): δ146.20,133.25,132.89,130.92,129.56,126.33,122.34,116.16,115.59,115.40,112.43,73.70,58.23.

[0182] The NMR boron spectrum data of the product prepared in Example 12, 11 B{ 1 H}NMR(128MHz, CDCl3)δ-2.36(1B),-3.26(1B),-8.10(1B),-9.26(2B),-11.32(2B),-12.82(2B),-14.12(1B).

[0183] Mass spectrometry data (HRMS (ESI)) m / z) of the product prepared in Example 12: Theoretical value [MH] - C 13 H 15 B 10 Cl2N2 - 379.1543; Actual value 379.1548.

[0184] Example 13

[0185] The carborane derivative of this embodiment has the following structural formula:

[0186]

[0187] Its preparation method includes the following steps:

[0188] 0.19 g (1 mmol) of 1-aldehyde-2-methylo-carborane, 0.16 g (1 mmol) of 2-(1H-pyrrolo-1-yl)aniline, and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of boron trifluoride ether was added with stirring. The mixture was stirred at 65 °C for 3 h. 20 mg (0.2 mmol) of triethylamine was added with stirring, followed by 0.39 g (1.2 mmol) of iodophenyldiacetic acid. The mixture was stirred for 10 min. The reaction solution was filtered, and the filter cake was washed with chloroform and dried to give 0.24 g of a yellow solid with a yield of 75% and a melting point of 146-148 °C.

[0189] The 1H NMR spectrum data of the product prepared in Example 13 1 H NMR (400MHz, CDCl3): δ8.03 (dd, J=2.8, 1.1Hz, 1H), 8.00 (dd, J=8.1, 1.3Hz, 1H), 7.88 (dd, J=8.3, 1.0H z,1H),7.61(ddd,J=8.4,7.3,1.5Hz,1H),7.51-7.46(m,2H),6.97(dd,J=4.3,2.8Hz,1H),1.84(s,3H).

[0190] The carbon NMR spectrum data of the product prepared in Example 13, 13 C{ 1 H}NMR (101MHz, CDCl3): δ142.52,134.32,130.99,129.67,126.99,125.62,124.15,115.06,114.44,113.58,111.09,79.68,78.72,23.58.

[0191] The NMR boron spectrum data of the product prepared in Example 13, 11 B{ 1 H} NMR (128MHz, CDCl3) δ -1.43 (d, J = 146.2Hz, 1B), -5.43 (d, J = 143.9Hz, 1B), -9.54 (4B), -10.59 (4B).

[0192] Mass spectrometry data of the product prepared in Example 13: HRMS (ESI) m / z: theoretical value [M+H] + C 14 H 21 B 10 N2 + 327.2635; Actual value 327.2630.

[0193] Example 14

[0194] The carborane derivative of this embodiment has the following structural formula:

[0195]

[0196] Its preparation method includes the following steps:

[0197] 0.25 g (1 mmol) of 1-aldehyde-2-phenyl-o-carborane (the preparation process can be found in the method disclosed in J. Org. Chem., 2024, 89, 3573), 0.16 g (1 mmol) of 2-(1H-pyrrolo-1-yl)aniline, and 7.4 g of chloroform were added to a reaction flask. 14 mg (0.1 mmol) of boron trifluoride ether was added under stirring. The mixture was stirred at 65 °C for 3 h. 20 mg (0.2 mmol) of triethylamine was added and stirred. Then 0.39 g (1.2 mmol) of iodophenyldiacetic acid was added and stirred for 8 min. The reaction solution was filtered, and the filter cake was washed with chloroform and dried to give 0.26 g of a yellow solid with a yield of 68% and a melting point of 220-222 °C.

[0198] The 1H NMR spectrum data of the product prepared in Example 14 1 H NMR (400MHz, CDCl3): δ7.87(dd,J=2.7,1.0Hz,1H),7.75(dd,J=8.1,1.3Hz,1H),7.70(d,J=8.3Hz,1H),7 .61-7.56(m,2H),7.50-7.44(m,2H),7.39-7.33(m,1H),7.13-7.02(m,3H),6.90(dd,J=4.3,2.8Hz,1H).

[0199] The carbon NMR spectrum data of the product prepared in Example 14 13 C{ 1 H}NMR (101MHz, CDCl3): δ141.95,133.97,131.08,130.99,130.55,129.90,129.28 ,127.88,126.62,125.35,124.11,114.72,114.15,113.39,110.24,86.70,82.96.

[0200] The NMR boron spectrum data of the product prepared in Example 14, 11 B{ 1 H} NMR (128MHz, CDCl3) δ -0.86 (d, J = 149.5Hz, 1B), -3.26 (d, J = 151.2Hz, 1B), -9.60 (4B), -10.64 (4B).

[0201] Mass spectrometry data (HRMS(ESI) m / z) of the product prepared in Example 14: Theoretical value [M+H] + C 19 H 23 B 10 N2 +389.2792; Actual value 389.2784.

[0202] II. Optical Application Testing

[0203] 1. Luminescence test in solid state

[0204] The solid compounds obtained in Examples 1-14 were respectively irradiated under sunlight and 365nm ultraviolet light. Figure 7 As can be seen, compared with fluorescent light, the irradiated compound displays full-color light, including blue, green, yellow, orange, red and white light, and has good optical effects. It can be applied to organic light-emitting materials fields such as full-color display technology, organic light-emitting diodes, and advanced information encryption for LED displays.

[0205] 2. Optical data testing

[0206] The maximum excitation and emission wavelengths of the compounds in Table 1 in the solid state were measured using a fluorescence spectrometer. The data in Table 1 show that the compound prepared by carborane and pyrrole / indolequinoxaline has a larger Stokes shift value than the conventional compound 7-fluoro-4-benzylpyrrolo[1,2-a]quinoline in Comparative Example 1. This increased value can prevent self-absorption or "internal filter" effects, thereby improving the signal-to-noise ratio of fluorescence imaging, making this property very useful in fluorescence applications.

[0207] Table 1: Fluorescence test data of Examples 4 and 11

[0208]

[0209] 3. Aggregation-Induced Emission (AIE) Effect Test

[0210] The compound was dissolved in different aqueous solutions of tetrahydrofuran to prepare solutions with a concentration of 3 × 10⁻⁶. -5 Solutions with a concentration of mol / L and water contents of 0%, 80%, or 90% were prepared. The compound had good solubility in tetrahydrofuran but was insoluble in aqueous solution. When the water content of the solution increased, the compound aggregated. The series of solutions were irradiated with a UV lamp to observe the different luminescence patterns during dissolution and aggregation, and the fluorescence emission intensity was measured. Figure 8 , 9 Fluorescence emission spectra of compounds in Examples 4 and 11 in solutions with different water contents are presented. According to... Figure 8 , Figure 9 The fluorescence emission spectrum shows that the fluorescence intensity increases when the water content is around 90%, i.e., when aggregation occurs.

[0211] Figure 10The emission patterns of Examples 1-3 and Examples 5-7 under 365nm ultraviolet light at 0%-80% water content are given; Figure 11 The emission patterns of Examples 8-10 and 12 under 365nm ultraviolet light at 0%-80% moisture content and Examples 13-14 under 365nm ultraviolet light at 0%-90% moisture content are given. Figure 10 , Figure 11 It can be clearly seen that the solution with high water content has stronger fluorescence than the solution with low water content, exhibiting a good "aggregation-induced emission" effect. Figure 12 The fluorescence emission spectra of Comparative Example 2 in different solutions; Figure 13 This is the emission diagram of Comparative Example 2 under 365nm ultraviolet light in different solutions; from Figure 12 and Figure 13 It can be seen that when compound 10-fluoro-6-phenylindo[1,2-a]quinoxaline of Comparative Example 2 is aggregated in a solution with high water content, the fluorescence intensity decreases sharply.

[0212] Comparative Example 2 Compound:

[0213]

[0214] Compared with Comparative Example 2, the compound of the present invention exhibits a good aggregation-induced emission effect and is a potential aggregation-induced emission material for application in the field of organic light-emitting materials.

[0215] 4. Application testing as an information encryption or anti-counterfeiting material

[0216] The compounds obtained in Examples 1-14 were dissolved in tetrahydrofuran to prepare solutions with a concentration of 0.1 mol / L. Filter paper strips were immersed in the solutions, dried, and observed under fluorescent and 365 nm ultraviolet lamps, respectively. Figure 14 , Figure 15 It can be seen that the filter paper strips soaked in the sample solution show no color under fluorescent light, but exhibit different colors such as blue, green, orange, and red under 365nm ultraviolet light. This solution can be coated onto a membrane in the form of patterns or text, and the corresponding patterns can be displayed under fluorescent illumination. This can be applied to the field of information encryption or used in combination with one or more compounds in the field of anti-counterfeiting materials.

[0217] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any equivalent structural changes made based on the description and drawings of the present invention should also be included within the scope of protection of the present invention.

Claims

1. A carborane derivative, characterized by, The carborane derivative is a compound represented by Formula I; wherein A ring is an aromatic ring or is absent; R 1 independently selected from H, C 1-3 any one of alkyl, aryl; R 2 is a substituent for any position of the aromatic ring, independently selected from H, C 1-3 alkyl, halogen, any one of; R 3 independently selected from H, C 1-3 alkyl; R 4 is a substituent for any position of the aromatic ring, independently selected from H, C 1-3 alkyl, halogen.

2. The carborane derivative according to claim 1, characterized in that, when said A ring is an aromatic ring, said R 1 , R 2 is selected from H; said R 3 independently selected from H, C 1-3 any one of alkyl; The R 4 Substituents at any position on the aromatic ring, independently selected from H, C 1-3 Any one of alkyl, -F, -Cl, and -Br.

3. The carborane derivative according to claim 1, wherein when the A ring is absent, the R 4 absent; said R 1 independently selected from H, C 1-3 any one of alkyl, phenyl; The R 2 It can be a substituent at any position on the aromatic ring, independently selected from H, -CH3, -F, and -Cl; said R 3 selected from H.

4. The carborane derivative according to claim 1 or 2, characterized by When ring A is an aromatic ring, the carborane derivative includes any one of the following compounds:

5. The carborane derivative according to claim 1 or 3, wherein When the A ring is absent, the carborane derivative includes any one of the following compounds:

6. A method for preparing a carborane derivative as described in any one of claims 1 to 5, characterized in that, The preparation method includes the following steps: The aldehyde-based o-carborane derivative of Formula II, the compound of Formula III, and Lewis acid were reacted in a solvent at 30–80 °C for 1.5–4 h, and then reacted with triethylamine and an oxidant for 2–60 min to obtain the compound of Formula I.

7. The method for preparing carborane derivatives according to claim 6, characterized in that, The Lewis acid includes any one of boron trifluoride ether, metal halide, p-toluenesulfonic acid, phosphoric acid, magnesium sulfate, and trifluoroacetic acid; the solvent includes any one of acetonitrile, toluene, and chloroalkanes, and the mass ratio of the aldehyde-based o-carborane derivative to the solvent is 1:(17-60); the oxidant is any one of potassium permanganate, [bis(trifluoroacetoxy)iodo]benzene, 2,3-dichloro-5,6-dicyanobenzoquinone, and iodophenyldiacetic acid; the molar ratio of the aldehyde-based o-carborane derivative, the compound of formula III, the Lewis acid, triethylamine, and the oxidant is 1:(0.8-1.2):(0.05-0.2):(0.1-0.3):(1-1.5).

8. The method for preparing carborane derivatives according to claim 7, characterized in that, The metal halide is selected from one of tin dichloride or its hydrate, aluminum trichloride, and zinc chloride; the chloroalkane is selected from one of dichloromethane, trichloromethane, and dichloroethane.

9. The use of any one of the carborane derivatives as described in claims 1 to 5 in organic light-emitting materials.

10. The application according to claim 9, characterized in that, The applications of organic light-emitting materials include those in organic light-emitting diodes, LED displays, anti-counterfeiting materials, and information encryption.

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