阅读说明：本技术 一种基于碳硼烷的静水压力荧光传感材料及其制备方法和应用 (Hydrostatic pressure fluorescent sensing material based on carborane, and preparation method and application thereof ) 是由 吕春燕 张玉建 杨圣晨 孙璟玮 曹枫 于 2021-08-03 设计创作，主要内容包括：本发明公开了一种基于碳硼烷的静水压力荧光传感材料及其制备方法和应用,该材料分子式为C-(22)H-(24)B-(10),以菲硼酸和4-邻碳硼烷溴苯为原料,通过Suzuki偶联反应制得。该材料可作为力致荧光变色压力传感探针,克服传统材料力致荧光淬灭的问题,在较低压力下呈现力致荧光增强性质,在压力传感系统的有着巨大应用潜力。(The invention discloses a carborane-based hydrostatic pressure fluorescent sensing material, and a preparation method and application thereof, wherein the molecular formula of the material is C 22 H 24 B 10 The compound is prepared by taking phenanthrene boric acid and 4-o-carborane bromobenzene as raw materials through Suzuki coupling reaction. The material can be used as a force-induced fluorescence color-changing pressure sensing probe, overcomes the problem of force-induced fluorescence quenching of the traditional material, shows the force-induced fluorescence enhancement property under lower pressure, and has great application potential in a pressure sensing system.)

1. The hydrostatic pressure fluorescence sensing material based on carborane is characterized in that the hydrostatic pressure fluorescence sensing material is carborane derivatives, and the molecular formula is as follows: c₂₂H₂₄B₁₀The structural formula is shown as the formula (III):

2. the preparation method of the hydrostatic pressure fluorescent sensing material as claimed in claim 1, characterized in that 4-o-carborane bromobenzene, phenanthreneboronic acid, palladium tetratriphenylphosphine and sodium carbonate are dissolved in tetrahydrofuran, heated to react under the protection of nitrogen atmosphere, extracted with water and pure dichloromethane after the reaction is completed, an extract phase is collected, dried and purified to obtain white powder, namely the target product carborane derivative (III).

3. The preparation method according to claim 2, wherein the molar ratio of the 4-o-carborane bromobenzene to the phenanthreneboronic acid to the tetrakistriphenylphosphine palladium to the sodium carbonate is 1: 1.0-1.5: 0.08-0.1: 0.8-1.0.

4. The preparation method according to claim 2, wherein the molar concentration of the 4-o-carborane bromobenzene and the tetrahydrofuran is 1/(30-45) mmol/ml.

5. The method of claim 2, wherein the purification is by column chromatography, and wherein the eluent comprises petroleum ether and dichloromethane in a volume ratio of 8: 1.

6. Use of carborane derivatives of formula (III) according to claim 1 in pressure sensors.

Technical Field

The invention belongs to the technical field of chemistry, and particularly relates to a carborane-based hydrostatic pressure fluorescent sensing material and a preparation method and application thereof.

Background

Pressure (force) induced color change refers to the phenomenon that the fluorescence color or/and intensity and the like are reversibly changed under the action of external mechanical force (friction, shearing and the like) or hydrostatic pressure. The hydrostatic pressure Photochromic (PCF) material has great application potential in the fields of pressure sensing systems (such as deep sea diving devices, aircraft wind tunnel tests and the like), optical recording, anti-counterfeiting, information display and storage and the like because the fluorescence of the material can be continuously changed under the action of pressure.

The traditional organic luminescent material increases the intermolecular interaction force under the action of static pressure, enhances the pi-pi action and finally leads to fluorescence quenching. In other words, the luminescence intensity of the molecule is continuously reduced under the action of hydrostatic pressure, which reduces the sensitivity of the pressure sensing device. Therefore, the construction of the hydrostatic pressure fluorescence enhancement material is the key to the detection line and sensitivity of the improved pressure sensing. Then, to date, the amount of hydrostatic pressure induced fluorescence enhancing material is still very small.

Disclosure of Invention

The invention aims to provide a carborane-based hydrostatic pressure fluorescence sensing material, a preparation method and application.

In order to achieve the technical purpose, the invention specifically adopts the following technical scheme:

the hydrostatic pressure fluorescent sensing material based on carborane is carborane derivative, and the chemical molecular formula of the material is C₂₂H₂₄B₁₀The structural formula is as follows:

in another aspect of the present invention, there is provided a process for the preparation of carborane derivatives of formula (III) above, comprising the steps of:

dissolving 4-o-carborane bromobenzene, phenanthrene boric acid, palladium tetratriphenylphosphine and sodium carbonate in tetrahydrofuran; stirring and reacting at 90-100 ℃ for 18-24 h under the protection of nitrogen atmosphere, after the raw materials react completely, extracting with water and pure dichloromethane for several times, collecting an extract phase, drying and purifying to obtain white powder, namely the carborane derivative (III) serving as the target product.

Further, the molar ratio of the 4-o-carborane bromobenzene to the phenanthrene boric acid to the tetrakistriphenylphosphine palladium to the sodium carbonate is 1: 1.0-1.5: 0.08-0.1: 0.8-1.0.

Further, the molar concentration of the 4-o-carborane bromobenzene and the tetrahydrofuran is 1/(30-45) mmol/ml.

Further, column chromatography is adopted for purification, wherein an eluent is composed of petroleum ether and dichloromethane according to the volume ratio of 8: 1.

Further, the carborane derivative powder is placed in a pressure test chamber for pressure sensing performance test.

In another aspect of the invention, there is provided the use of the carborane derivative (III) in a pressure sensor, preferably a hydrostatic pressure sensor.

The crystal powder of carborane derivative (III) of the present invention emits green fluorescence, and the luminance of the fluorescence increases with increasing pressure (1atm to 1.1gPa), and the luminance of the crystal also increases.

The invention has the beneficial effects that:

the method is characterized in that phenanthrene boric acid and 4-carborane bromobenzene are coupled to form carborane derivatives (III) through Suzuki coupling reaction, crystal powder of the carborane derivatives (III) emits green fluorescence under normal pressure, the fluorescence brightness is continuously increased along with the increase of pressure (1atm-1.1gPa), the brightness of the crystals is also continuously increased, the problem of fluorescence quenching caused by the force of a traditional material is solved, the fluorescence enhancement property caused by the force is presented under lower pressure, and the method has great application potential in a pressure sensing system.

Drawings

FIG. 1 is a single crystal spectrum of the molecular structure of carborane derivatives of the present invention;

FIG. 2 is a fluorescent photograph of carborane derivative crystals in the material of the present invention at a pressure in the range of 1atm to 1.1 gPa;

FIG. 3 is a luminescence spectrum of a carborane derivative (III) crystal of the present invention at a pressure range of 1atm to 1.1 gPa.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a carborane-based hydrostatic pressure fluorescent sensing material, which is prepared by the following steps:

the synthetic route is as follows:

weighing 4-o-carborane bromobenzene (I), phenanthreneboronic acid (II), palladium tetratriphenylphosphine and sodium carbonate, and dissolving in tetrahydrofuran; wherein, the 4-carborane bromobenzene (I): phenanthreneboronic acid (II): palladium tetratriphenylphosphine: sodium carbonate: 1 to 1.5mmol of 0.08 to 0.1mmol of 0.8 to 1mmol of 30 to 45mL of tetrahydrofuran;

heating and stirring at 90-100 ℃ for reaction for 18-24 h under the protection of nitrogen atmosphere; determining the reaction process by Thin Layer Chromatography (TLC), extracting the reaction system for three times by using a water and dichloromethane system after the reaction is ended, collecting an extract phase, and purifying by using petroleum ether and dichloromethane 8:1 eluent for column chromatography to obtain white powder, namely a carborane derivative (III) as a target product, wherein the molecular weight of 4-carborane bromobenzene (I) is 299 g/mol; 222g/mol of phenanthreneboronic acid (II); 779g/mol of carborane derivative (III).

Example 1

A preparation method of a carborane-based pressure fluorescence sensing material comprises the following steps:

0.299g (1mmol) of 4-carborane bromobenzene (I), 0.222g (1mmol) of phenanthreneboronic acid (II), 0.091g (0.08mmol) of palladium tetrakistriphenylphosphine and 0.084g (0.8mmol) of sodium carbonate are weighed and dissolved in 30mL of tetrahydrofuran; heating and stirring at 90 ℃ for reacting for 18h under the protection of nitrogen atmosphere; meanwhile, the reaction progress is determined by combining Thin Layer Chromatography (TLC), after the reaction is stopped, the reaction system is extracted three times by using water and a dichloromethane system, and then column chromatography purification is carried out by using petroleum ether and dichloromethane eluent with the volume ratio of 8:1 to obtain 0.273g of white powder, wherein the yield is 35 percent, namely the target product carborane derivative (III).

The characterization data are as follows: 1H NMR (400MHz, Chloroform-d) δ 8.84(d, J ═ 2.0hz,1H),8.74(d, J ═ 8.1hz,1H),7.97(d, J ═ 8.2hz,1H),7.92(dd, J ═ 7.8,1.6hz,1H),7.78(d, J ═ 7.3hz,3H),7.74(d, J ═ 1.8hz,1H),7.72(d, J ═ 2.0hz,1H), 7.70-7.65 (m,1H),7.63(d, J ═ 2.4hz,2H),7.61(d, J ═ 2.2hz,1H),4.02(s,1H),2.74(d, J ═ 2H, 142H).

The single crystal structure of the molecule is shown in fig. 1, and it is known that the carborane derivative (III) prepared by the invention is a completely new structural substance.

Example 2

A preparation method of a carborane-based pressure fluorescence sensing material comprises the following steps:

0.299g (1mmol) of 4-carborane bromobenzene (I), 0.267g (1.2mmol) of phenanthreneboronic acid (II), 0.091g (0.08mmol) of tetrakistriphenylphosphine palladium and 0.084g (0.8mmol) of sodium carbonate are weighed and dissolved in 30mL of tetrahydrofuran; heating and stirring at 90 ℃ for reacting for 18h under the protection of nitrogen atmosphere; meanwhile, the reaction progress is determined by combining Thin Layer Chromatography (TLC), after the reaction is ended, the reaction system is extracted three times by using a water and dichloromethane system, and then column chromatography purification is carried out by using petroleum ether and dichloromethane 8:1 eluent, so that 0.288g of white powder is obtained, and the yield is 37%, namely the target product carborane derivative (III).

Example 3

A preparation method of a carborane-based pressure fluorescence sensing material comprises the following steps:

0.299g (1mmol) of 4-carborane bromobenzene (I), 0.244g (1.1mmol) of phenanthreneboronic acid (II), 0.091g (0.8mmol) of tetrakistriphenylphosphine palladium and 0.084g (0.8mmol) of sodium carbonate are weighed and dissolved in 40mL of tetrahydrofuran; heating and stirring at 100 ℃ for reacting for 18h under the protection of nitrogen atmosphere; meanwhile, the reaction progress is determined by combining Thin Layer Chromatography (TLC), after the reaction is ended, the reaction system is extracted three times by using a water and dichloromethane system, and then column chromatography purification is carried out by using petroleum ether and dichloromethane 8:1 eluent, so that 0.280g of white powder is obtained, the yield is 36%, and the target product carborane derivative (III) is obtained.

Example 4

A preparation method of a carborane-based pressure fluorescence sensing material comprises the following steps:

0.299g (1mmol) of 4-carborane bromobenzene (I), 0.267g (1.2mmol) of phenanthreneboronic acid (II), 0.114g (0.1mmol) of palladium tetrakistriphenylphosphine and 0.105g (1mmol) of sodium carbonate are weighed and dissolved in 40mL of tetrahydrofuran; heating and stirring at 95 ℃ for reacting for 18h under the protection of nitrogen atmosphere; meanwhile, the reaction progress is determined by combining Thin Layer Chromatography (TLC), after the reaction is ended, the reaction system is extracted three times by using a water and dichloromethane system, and then column chromatography purification is carried out by using petroleum ether and dichloromethane 8:1 eluent, so that 0.312g of white powder is obtained, the yield is 40%, and the target product carborane derivative (III) is obtained.

Example 5

The white target product (III) prepared in example 3 was placed in a pressing chamber and the fluorescence spectra at different hydrostatic pressures were tested. As shown in fig. 2, the crystal fluorescence intensity increases with increasing hydrostatic pressure.

The white target product (III) prepared in example 4 was placed in a pressing chamber and tested for crystal fluorescence under different hydrostatic pressures. As shown in fig. 3, the intensity of the fluorescence spectrum increases with increasing hydrostatic pressure.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.