CN110304982B

CN110304982B - Pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement function and synthesis method and application thereof

Info

Publication number: CN110304982B
Application number: CN201910203632.0A
Authority: CN
Inventors: 王传增; 赵文暄; 郭福衡; 曾照轩; 大和武彦
Original assignee: Shandong University of Technology
Current assignee: Shandong University of Technology
Priority date: 2019-03-18
Filing date: 2019-03-18
Publication date: 2022-04-12
Anticipated expiration: 2039-03-18
Also published as: CN110304982A

Abstract

The invention discloses a pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement and a synthesis method and application thereof, wherein R in the pyrenyl hexa-substituted benzene compound is one of hydrogen atom, tertiary butyl, methoxy, trifluoromethyl, cyano and aldehyde group, and the series of compounds have potential application values in the fields of luminescent materials, chemical sensing, bioluminescence probes, biological imaging and detection; the synthesis method has the advantages that the raw materials are simple to prepare, the performance is very stable, and special storage conditions are not needed; related reagents and solvents are common commercial reagents, so that the cost is low; the whole synthesis route is simple, the yield is high, and the pollution is less; the synthesis method comprises three steps of synthesis, extraction and purification, simplifies the synthesis steps compared with the traditional aggregation-induced emission compound, and is easier to be applied and popularized industrially.

Description

Pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement function and synthesis method and application thereof

Technical Field

The invention belongs to the technical field of luminescent materials, and particularly relates to a pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, and a synthesis method and application thereof.

Background

Aggregation-induced emission (AIE) is an unconventional photophysical phenomenon discovered in 2001 by down loyalty professor: some propeller-like molecules do not or weakly emit light in solution, while the emitted light intensity is significantly increased in the aggregated state. And further arouses the interest of scientific researchers worldwide. Currently, most AIE systems are also focused on derivative compounds based on the structure of tetraphenylethylene or tetraphenylethylene-like structures, and the synthesis of other types of structural systems with AIE properties remains to be explored. Particularly, the pyrenyl AIE system is relatively rare to synthesize, although pyrene occupies an important position in the research of photoelectric functional materials, due to a large plane conjugated structure, pi-pi accumulation is easily formed, and fluorescence quenching occurs in an aggregation state.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, and the series of compounds have greater application potential in the fields of luminescent materials, biological imaging or detection and the like; the invention takes 7-tert-butyl-1-benzene alkynyl pyrene compounds and tetraphenyl cyclopentadienone as raw materials, prepares a series of pyrenyl hexa-substituted benzene compounds by Diels-Alder reaction (D-A reaction) under the heating condition, and provides a new method for synthesizing pyrenyl aggregation induced fluorescence enhancement compounds.

In order to expand the compound types of the traditional aggregation-induced emission system, the structural formula of the pyrenyl hexasubstituted benzene compound with aggregation-induced emission enhancement is as follows:

wherein R is one of hydrogen atom, tertiary butyl, methoxyl, trifluoromethyl, cyano and aldehyde group. The pyrenyl hexa-substituted benzene compound has the property of aggregation-induced emission enhancement and has the potential of being applied to the fields of luminescent materials or biological imaging, detection and the like.

In order to better prepare the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, the technical scheme of the invention provides a synthesis method of the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, which comprises the following steps:

s1, synthesizing, namely, preparing the pyrenyl hexa-substituted benzene compound by carrying out Diels-Alder reaction (D-A reaction) on the 7-tert-butyl-1-phenylalkynyl pyrene compound and tetraphenylcyclopentadienone, wherein the reaction formula is as follows:

s2, extracting, after the reaction is finished, extracting the cooled reaction product for 2-3 times by using a good solvent, collecting an organic phase solution, washing the collected organic phase solution for 2-3 times by using saturated salt solution in sequence, and drying by using anhydrous magnesium sulfate to obtain a mixed solution of a reaction crude product and the good solvent;

and S3, purifying, namely distilling and carrying out column chromatography on the mixed solution of the reaction crude product and the good solvent in sequence to obtain a pure target product.

The raw materials used in the invention are simple to prepare, have very stable performance and do not need special storage conditions; related reagents and solvents are common commercial reagents, so that the cost is low; the whole synthesis route is simple, the yield is high, and the pollution is less.

In order to better prepare the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, the preferable technical scheme is that in the step S1, the molar ratio of the 7-tert-butyl-1-phenylalkynyl pyrene compound to the tetraphenylcyclopentadienone is 1: 1-2, the solvent is diphenyl ether, the reaction temperature is 200-260 ℃, and the reaction time is 12-36 hours.

In order to improve the utilization rate of raw materials and the reaction efficiency, a further preferable technical scheme is that in the step S1, the molar ratio of the 7-tert-butyl-1-phenylalkynyl pyrene compound to the tetraphenylcyclopentadienone is 1: 1.5, the solvent is diphenyl ether, the reaction temperature is 260 ℃, and the reaction time is 24 hours.

In order to improve the extraction efficiency of the reaction product, a preferred technical scheme is that the good solvent in the step S2 is dichloromethane.

In order to improve the purification efficiency, the preferable technical scheme is that the stationary phase used in the column chromatography in the step S3 is silica gel, the eluent is a mixed solution of dichloromethane and n-hexane, and the volume ratio of dichloromethane to n-hexane is 1: 1.5-9.

In order to further improve the purification efficiency of the product, a more preferable technical scheme is that the eluent used in the column chromatography in the step S3 is a mixed solution of dichloromethane and n-hexane, and the volume ratio of the two is optimal for different products.

In order to better popularize and apply the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, the application of the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement in the fields of luminescent materials, chemical sensing, biological fluorescent probes, biological imaging and detection is provided.

The invention has the advantages and beneficial effects that:

1. the invention provides a pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, which expands the variety of the traditional aggregation-induced emission system; the series of compounds have potential application values in the fields of luminescent materials, chemical sensing, biological fluorescent probes, biological imaging and detection.

2. The invention takes 7-tert-butyl-1-benzene alkynyl pyrene compounds and tetraphenyl cyclopentadienone as raw materials, prepares a series of pyrenyl hexa-substituted benzene compounds by Diels-Alder reaction (D-A reaction) under the heating condition, and provides a new method for synthesizing pyrenyl aggregation induced fluorescence enhancement compounds.

3. The raw materials used in the synthesis method are simple to prepare, have very stable performance and do not need special storage conditions; related reagents and solvents are common commercial reagents, so that the cost is low; the whole synthesis route is simple, the yield is high, and the pollution is less; the synthesis method comprises three steps of synthesis, extraction and purification, simplifies the synthesis steps compared with the traditional aggregation-induced emission compound, and is easier to be applied and popularized industrially.

Drawings

FIG. 1 is a structural formula of a pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement according to the present invention;

FIG. 2 is a chemical reaction formula for synthesizing pyrenyl hexa-substituted benzenes with aggregation-induced emission enhancement according to the present invention;

FIG. 3 is a chemical reaction formula for synthesizing 1,2,3,4, 5-pentaphenyl-6- (7 '-tert-butyl-1' -pyrenyl) benzene (a) of example 1;

FIG. 4 is a single crystal structural view of the objective product b of example 8;

FIG. 5 is a single crystal structural view of a target product c of example 9;

FIG. 6 is the fluorescence emission spectrum of the target product a in different volume ratios of solutions (water and tetrahydrofuran) in example 1;

FIG. 7 is a graph comparing the peak values of the maximum fluorescence emission intensities of the target product a in different volume ratios of solutions (water and tetrahydrofuran) in example 1;

FIG. 8 is a graph comparing the peak values of the maximum fluorescence emission intensities of the target product b of example 8 in solutions (water and tetrahydrofuran) at different volume ratios;

FIG. 9 is a graph comparing the peak values of the maximum fluorescence emission intensities of the target product c of example 9 in solutions (water and tetrahydrofuran) at different volume ratios;

FIG. 10 is a graph comparing the peak values of the maximum fluorescence emission intensities of the target product d of example 10 in solutions (water and tetrahydrofuran) at different volume ratios;

FIG. 11 is a graph comparing the peak values of the maximum fluorescence emission intensities of the target product e of example 11 in different volume ratios of solutions (water and tetrahydrofuran);

FIG. 12 is a graph comparing the peak values of the maximum fluorescence emission intensity of the target product f of example 12 in different volume ratios of solutions (water and tetrahydrofuran).

Detailed Description

The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby. The procedures, conditions, reagents, test methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited. The data given in the examples below include specific operating and reaction conditions and products. The purity of the product is identified by nuclear magnetism and high-resolution mass spectrometry, and accurate structural information of partial compounds is obtained by an X-ray single crystal diffractometer.

A pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement has a structural formula shown as follows:

wherein R is one of hydrogen atom, tertiary butyl, methoxyl, trifluoromethyl, cyano and aldehyde group.

The synthesis method of the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement comprises the following steps:

Example 1

Taking a synthesis example of 1,2,3,4, 5-pentaphenyl-6- (7 '-tert-butyl-1' -pyrenyl) benzene, the chemical reaction formula is shown as follows.

To a 5mL eggplant type bottle were added phenylalkynylpyrene (100 mg, 0.279 mmol), tetraphenylcyclopentadienone (161 mg, 0.419 mmol), followed by the solvent diphenyl ether (1.0 mL). The reaction is carried out by heating through an electric heating sleeve, the temperature is controlled at 260 ℃, and the reaction reflux is carried out for 24 hours. After completion of the reaction, the reaction mixture was extracted twice with 20 mL of methylene chloride, washed twice with 20 mL of saturated brine, and dried over an appropriate amount of anhydrous magnesium sulfate. After the solution is distilled to a small amount of residual liquid, a white solid target product a is isolated by column chromatography with a dichloromethane/n-hexane mixed solution (1: 9, volume ratio) as eluent, with a yield of 95.7 mg (theoretical yield of target product of 0.279 mmol × 714 g/mol =199.2 mg) and a yield of 48%. The melting point of the target product a is measured to be 318-320 ℃;

¹H NMR (400 MHz, CDCl₃): δ_H = 1.55 (s, 9H, tBu), 6.38 (t, J = 7.5 Hz, 2H, Ph-H), 6.48 (t, J = 7.4 Hz, 2H, Ph-H), 6.63 (t, J = 7.4 Hz, 2H, Ph-H), 6.70 (d, J = 7.5 Hz, 2H, Ph-H), 6.83–6.98 (m, 17H, Ph-H), 7.64 (d, J = 7.9 Hz, 1H, pyrene-H), 7.73 (d, J = 7.9 Hz, 1H, pyrene-H), 7.79 (d, J = 9.0 Hz, 1H, pyrene-H), 7.86 (d, J = 9.0 Hz, 1H, pyrene-H), 7.91 (d, J = 9.3 Hz, 1H, pyrene-H), 8.06 (d, J = 9.2 Hz, 1H, pyrene-H), 8.10 (s, 1H, pyrene-H), 8.11 ppm (s, 1H, pyrene-H);

¹³C NMR (100 MHz, CDCl₃): δ_C= 31.93, 35.14, 121.74, 121.90, 122.81, 123.24, 123.93, 125.12, 125.19, 125.23, 126.04, 126.35, 126.53, 126.57, 126.63, 127.39, 129.28, 129.38, 129.54, 130.34, 130.70, 130.91, 131.03, 131.45, 131.51, 131.56, 136.27, 138.78, 140.27, 140.42, 140.60, 140.73, 141.52, 148.56 ppm;

FAB-MS: m/z calcd for C₅₆H₄₂ 714.3287 [M⁺]; found 714.3266 [M⁺]。

example 2

Example 2 differs from example 1 in that phenylalkynylpyrene (100 mg, 0.279 mmol) and tetraphenylcyclopentadienone (107 mg, 0.279 mmol) were dosed and isolated in a yield of 61.8 mg and 31% as white solid of the desired product a, the data of which were determined in the same manner as in example 1.

Example 3

Example 3 differs from example 1 in that phenylalkynylpyrene (100 mg, 0.279 mmol) and tetraphenylcyclopentadienone (214 mg, 0.558 mmol) were dosed and isolated in 97.7 mg of the desired product a as a white solid with a yield of 49%, as determined in example 1.

Example 4

Example 4 differs from example 1 in that phenylalkynylpyrene (100 mg, 0.279 mmol) and tetraphenylcyclopentadienone (161 mg, 0.419 mmol) were charged, the reaction temperature was 200 ℃ and the isolated yield of the desired product a was 83.7 mg and 42% as a white solid, and the test data were the same as in example 1.

Example 5

Example 5 differs from example 1 in that phenylalkynylpyrene (100 mg, 0.279 mmol) and tetraphenylcyclopentadienone (161 mg, 0.419 mmol) were dosed and the reaction temperature was 240 ℃ and the isolated target product a was isolated in a yield of 89.7 mg and 45% as a white solid, according to the test data of example 1.

Example 6

Example 5 differs from example 1 in that phenylalkynylpyrene (100 mg, 0.279 mmol) and tetraphenylcyclopentadienone (161 mg, 0.419 mmol) were dosed and the reaction time was 12h, the isolated target product a was isolated in a yield of 59.8 mg and 30% yield as a white solid, the data of which were identical to example 1.

Example 7

Example 7 differs from example 1 in that phenylalkynylpyrene (100 mg, 0.279 mmol) and tetraphenylcyclopentadienone (161 mg, 0.419 mmol) were dosed and the reaction time was 36h, the isolated target product a was isolated in 97.7 mg yield of 49% as a white solid and the test data were the same as in example 1.

TABLE 1 reaction conditions and Experimental results for examples 1-7

The experimental results show that: the yields of the target products of the example 1 and the example 3 are higher than those of the example 2 and the examples 4-7, wherein the raw material input amount of the example 3 is large, so that the reaction conditions of the example 1 are determined to be optimal, namely the molar ratio of the phenylalkynyl pyrene to the tetraphenylcyclopentadienone is 1: 1.5, the reaction temperature is 260 ℃, and the reaction time is 24 hours.

Example 8

Example 8 is different from example 1 in that the R substituent in the 7-tert-butyl-1-phenylalkynyl pyrene compound is tert-butyl and the reaction conditions of example 1 are followed, the yield of the target product b obtained by separation is 88%, and the structure of the target product b is shown in FIG. 4. The melting point of the target product is 327-329 ℃ through measurement;

¹H NMR (400 MHz, CDCl₃): δ_H = 1.55 (s, 9H, tBu), 6.40 (t, J = 7.5 Hz, 2H, Ph-H), 6.48 (t, J = 7.4 Hz, 2H, Ph-H), 6.59 (t, J = 7.4 Hz, 2H, Ph-H), 6.72 (d, J = 7.5 Hz, 2H, Ph-H), 6.85–6.93 (m, 16H, Ph-H), 7.62 (d, J = 7.9 Hz, 1H, pyrene-H), 7.72 (d, J = 7.9 Hz, 1H, pyrene-H), 7.81 (d, J = 9.0 Hz, 1H, pyrene-H), 7.85 (d, J = 9.0 Hz, 1H, pyrene-H), 7.91 (d, J = 9.3 Hz, 1H, pyrene-H), 8.05 (d, J = 9.2 Hz, 1H, pyrene-H), 8.08 (s, 1H, pyrene-H), 8.10 ppm (s, 1H, pyrene-H);

¹³C NMR (100 MHz, CDCl₃): δ_C = 33.80, 35.13, 121.62, 121.72, 122.79 123.22, 123.95, 124.95, 125.05, 125.11, 125.16, 125.96, 126.30, 126.43, 126.53, 126.58, 126.66, 127.34, 129.29, 129.32, 129.60, 129.98, 130.50, 130.71, 130.94, 131.47, 131.58, 136.51, 137.14, 138.88, 140.15, 140.34, 140.54, 140.60, 140.70, 140.84, 141.37, 141.70, 147.58, 148.47 ppm;

FAB-MS: m/z calcd for C₆₀H₅₀ 770.3913 [M⁺]; found 770.3946 [M⁺]。

example 9

Example 9 is different from example 1 in that the R substituent in the 7-tert-butyl-1-phenylalkynyl pyrene compound is methoxy, the reaction conditions are the same as those in example 1, the yield of the white solid target product c obtained by separation is 72%, and the structural diagram of the target product c is shown in 5. The melting point of the target product is measured to be 281-283 ℃;

¹H NMR (400 MHz, CDCl₃): δ_H = 1.55 (s, 9H, tBu), 3.34 (s, 3H, OMe), 5.93 (dd, J = 8.4 Hz, 2H, Ph-H), 6.18 (dd, J = 8.5 Hz, 2H, Ph-H), 6.37 (t, 2H, Ph-H), 6.48 (t, 2H, Ph-H), 6.66 (t, J = 7.4 Hz, 2H, Ph-H), 6.75 (d, J = 7.5 Hz, 2H, Ph-H), 6.84–6.89 (m, 16H, Ph-H), 7.65 (d, J = 7.9 Hz, 1H, pyrene-H), 7.74 (d, J = 7.9 Hz, 1H, pyrene-H), 7.83 (d, J = 9.0 Hz, 1H, pyrene-H), 7.89 (d, J = 9.0 Hz, 1H, pyrene-H), 7.92 (d, J = 9.3 Hz, 1H, pyrene-H), 8.05 (d, J = 9.2 Hz, 1H, pyrene-H), 8.12 ppm (s, 2H, pyrene-H);

¹³C NMR (100 MHz, CDCl₃): δ_C =31.93, 35.14, 54.53, 111.74, 121.68, 121.84, 122.84, 123.31, 123.95, 125.08, 125.12, 125.16, 126.00, 126.30, 126.53, 126.61, 127.41, 129.22, 129.30, 129.51, 130.29, 130.70, 130.86, 131.02, 131.35, 131.42, 131.53, 131.86, 132.67, 136.45, 139.00, 140.20, 140.31, 140.63, 140.78, 141.09, 141.49, 148.52, 156.67 ppm;

FAB-MS: m/z calcd for C₅₇H₄₄O 744.3392 [M⁺]; found 744.3386 [M⁺]。

example 10

Example 10 is different from example 1 in that the R substituent in the 7-tert-butyl-1-phenylalkynyl pyrene compound is trifluoromethyl, which was conducted according to the reaction conditions of example 1, and the yield of the objective product d isolated as a white solid was 69%. The melting point of the target product d is measured to be 348 ℃ and 349 ℃;

¹H NMR (400 MHz, CDCl₃): δ_H = 1.55 (s, 9H, tBu), 6.39 (t, J = 7.3 Hz, 2H, Ph-H), 6.49 (t, J = 7.3 Hz, 2H, Ph-H), 6.63 (t, J = 7.6 Hz, 2H, Ph-H), 6.70 (d, J = 7.5 Hz, 2H, Ph-H), 6.78–6.93 (m, 16H, Ph-H), 7.62 (d, J = 7.7 Hz, 1H, pyrene-H), 7.74 (d, J = 7.6 Hz, 1H, pyrene-H), 7.81 (d, J = 8.7 Hz, 1H, pyrene-H), 7.91 (dd, J = 16.5 Hz, 2H, pyrene-H), 8.04 (d, J = 9.2 Hz, 1H, pyrene-H), 8.13 ppm (s, 2H, pyrene-H);

¹³C NMR (100 MHz, CDCl₃): δ_C= 31.92, 35.16, 110.03, 121.89, 122.15, 122.75, 123.07, 123.36, 123.94, 125.31, 126.39, 126.63, 126.69, 126.81, 126.93, 127.32, 129.26, 129.58, 130.26, 130.43, 130.60, 130.81, 131.03, 131.12, 131.27, 131.33, 131.38, 135.46, 138.56, 139.91, 140.01, 140.11, 140.32, 140.37, 140.94, 141.04, 141.76, 144.28 ppm;

FAB-MS: m/z calcd for C₅₇H₄₁F₃ 782.3160 [M⁺]; found 782.3147 [M⁺]。

example 11

Example 11 is different from example 1 in that the R substituent in the 7-tert-butyl-1-phenylalkynyl pyrene compound is cyano and the reaction conditions of example 1 are followed, and the yield of the isolated white solid target product e is 68%. The melting point of the target product e is measured to be 186-187 ℃;

¹H NMR (400 MHz, CDCl₃): δ_H = 1.59 (s, 9H, tBu), 6.44 (t, J = 7.4 Hz, 1H, Ph-H), 6.55 (t, J = 7.4 Hz, 1H, Ph-H), 6.68–6.77 (m, 3H, Ph-H), 6.82–7.04 (m, 19H, Ph-H), 7.64 (d, J = 7.8 Hz, 1H, pyrene-H), 7.78 (d, J = 7.9 Hz, 1H, pyrene-H), 7.84 (d, J = 8.9 Hz, 1H, pyrene-H), 7.91–7.99 (m, 2H, pyrene-H), 8.04 (d, J = 9.1 Hz, 1H, pyrene-H), 8.18 ppm (d, J = 2.7 Hz, 2H, pyrene-H);

¹³C NMR (100 MHz, CDCl₃): δ_C = 30.88, 34.13, 107.79, 117.80, 120.97, 121.32, 121.63, 122.34, 122.87, 124.37, 124.45, 124.70, 124.74, 125.18, 125.46, 125.64, 125.72, 125.91, 126.04, 126.11, 126.20, 128.08, 128.61, 128.91, 129.10, 129.19, 129.47, 129.73, 129.94, 130.18, 130.28, 130.40, 134.05, 137.40, 138.74, 138.95, 139.10, 140.00, 140.35, 140.80, 144.64, 147.83 ppm;

FAB-MS: m/z calcd for C₅₇H₄₁O 739.3239 [M⁺]; found 739.3235 [M⁺]。

example 12

Example 12 is different from example 1 in that the R substituent in 7-tert-butyl-1-phenylalkynyl pyrene compound is aldehyde group, and the yield of the target product f obtained by separation was 67% according to the reaction conditions of example 1. The melting point of the target product f is measured to be 170-171 ℃;

¹H NMR (400 MHz, CDCl₃): δ_H = 1.55 (s, 9H, tBu), 6.38–6.43 (m, 1H, Ph-H), 6.49–6.54 (m, 1H, Ph-H), 6.68 (d, J = 12.1 Hz, 3H, Ph-H), 6.80–6.98 (m, 19H, Ph-H), 7.63 (d, J = 7.8 Hz, 1H, pyrene-H), 7.73 (d, J = 7.7 Hz, 1H, pyrene-H), 7.79 (d, J = 8.9 Hz, 1H, pyrene-H), 7.88 (d, J = 8.9 Hz, 1H, pyrene-H), 7.93 (d, J = 9.2 Hz, 1H, pyrene-H), 8.04 (d, J = 11.2 Hz, 1H, pyrene-H), 8.12 (s, 2H, pyrene-H), 9.43 ppm (s, 1H, CHO-H);

¹³C NMR (100 MHz, CDCl₃): δ_C = 31.89, 35.14, 121.91, 122.16, 122.67, 123.33, 123.87, 125.29, 126.63, 126.70, 126.82, 126.90, 127.27, 128.93, 130.97, 131.24, 131.29, 131.35, 131.42, 133.00, 135.36, 138.42, 139.87, 139.93, 139.99, 140.24, 140.92, 141.13, 141.73, 147.33, 148.74, 192.02 ppm;

FAB-MS: m/z calcd for C₅₇H₄₂O 742.3236 [M⁺]; found 742.3260 [M⁺]。

TABLE 2 reaction conditions and Experimental results for examples 8 to 12

The experimental results show that: by adopting the synthesis method of the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement, the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement and with the substituents of tert-butyl, methoxy, trifluoromethyl, cyano and aldehyde can be successfully synthesized.

Example 13

The target compounds a to f in example 1 and examples 8 to 12 were tested for aggregation-induced emission properties:

the first step is as follows: the target compounds a to f in examples 1 and 8 to 12 were each prepared at a concentration of 5X 10^-711 parts of solution of mol/L, wherein the solvent is a mixture of water (poor solvent) and tetrahydrofuran (good solvent), and the volume ratio of the water to the tetrahydrofuran is 100: 0, 90: 10, 80: 20, 70: 30, 60: 40, 50: 50, 40: 60, 30: 70, 20: 80, 10: 90 and 1: 99 respectively;

the second step is that: and (3) respectively carrying out fluorescence test on 11 parts of solution of the target compounds a-f by using a fluorescence spectrum analyzer.

The experimental results show that: as shown in fig. 6, the peak value of the maximum fluorescence emission intensity of the target compound a gradually increases and then gradually decreases with the increase of the volume content of water in the solvent, wherein the peak value of the maximum fluorescence emission intensity occurs when the water content is 60%; as shown in fig. 7 to 12, the maximum fluorescence emission intensity peak values of the target compounds a to f gradually increase with the increase of the volume content of water in the solvent, the maximum fluorescence emission intensity peak values appear when the water content is 60%, and then the maximum fluorescence emission intensity peak values gradually decrease with the increase of the volume content of water in the solvent, which indicates that the target compounds a to f prepared by the synthesis method of the present invention all have aggregation-induced emission enhancement effects.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. The pyrenyl hexa-substituted benzene compound with the aggregation-induced emission enhancement function is characterized in that the structural formula is as follows:

2. The method for synthesizing the pyrenyl hexasubstituted benzenes compounds with aggregation-induced emission enhancement as recited in claim 1, comprising the steps of:

3. The method for synthesizing the pyrenyl hexasubstituted benzenes compound with aggregation-induced emission enhancement as claimed in claim 2, wherein the molar ratio of the 7-tert-butyl-1-phenylalkynyl pyrene compound to the tetraphenylcyclopentadienone in step S1 is 1: 1-2, the solvent is diphenyl ether, the reaction temperature is 200-260 ℃, and the reaction time is 12-36 h.

4. The method for synthesizing the pyrenyl hexasubstituted benzenes compound with aggregation induced emission enhancement as claimed in claim 3, wherein the molar ratio of the 7-tert-butyl-1-phenylalkynyl pyrene compound to the tetraphenylcyclopentadienone in step S1 is 1: 1.5, the solvent is diphenyl ether, the reaction temperature is 260 ℃, and the reaction time is 24 hours, so that the reaction efficiency is highest.

5. The method for synthesizing the pyrenyl hexasubstituted benzenes compounds with aggregation-induced emission enhancement as claimed in claim 4, wherein the good solvent in step S2 is dichloromethane.

6. The method for synthesizing the pyrenyl hexasubstituted benzenes compound with aggregation-induced emission enhancement as claimed in claim 5, wherein the stationary phase used in the column chromatography in step S3 is silica gel, the eluent is a mixture of dichloromethane and n-hexane, and the volume ratio of dichloromethane to n-hexane is 1: 1.5-9.

7. The application of the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement in the fields of chemical sensing, biological fluorescent probes and biological imaging, wherein the pyrenyl hexa-substituted benzene compound with aggregation-induced emission enhancement in the claim 1 is used for the fields of chemical sensing, biological fluorescent probes and biological imaging.