阅读说明：本技术 八元瓜环及烷基链调控的超分子多色荧光材料的制备方法 (Preparation method of supramolecular multicolor fluorescent material regulated and controlled by eight-membered cucurbituril and alkyl chain ) 是由 李佳琦 张晓东 周桂林 倪新龙 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种八元瓜环及烷基链调控的超分子多色荧光材料的制备方法,是以荧光分子2,5-二(4-吡啶乙烯)甲苯衍生物为客体分子,溶于水后,加入主体分子八元瓜环形成超分子自组装体,根据加入的2,5-二(4-吡啶乙烯)甲苯衍生物的不同以及加入的八元瓜环的量的不同,制备不同荧光的荧光材料。本发明能够通过调控制备不同颜色的荧光材料,且操作简单,易于生产。(The invention discloses a preparation method of a supermolecule multicolor fluorescent material regulated by eight-membered cucurbituril and an alkyl chain, which takes a fluorescent molecule 2, 5-di (4-pyridylethylene) toluene derivative as an object molecule, is dissolved in water, is added with a host molecule octatomic cucurbituril to form a supermolecule self-assembly body, and fluorescent materials with different fluorescence are prepared according to the difference of the added 2, 5-di (4-pyridylethylene) toluene derivative and the difference of the added octatomic cucurbituril. The invention can prepare fluorescent materials with different colors by regulation and control, and has simple operation and easy production.)

1. A preparation method of an eight-membered cucurbituril and alkyl chain regulated supramolecular multicolor fluorescent material is characterized by comprising the following steps: fluorescent molecule 2, 5-di (4-pyridine ethylene) toluene derivative is taken as guest molecule, after being dissolved in water, the host molecule eight-membered cucurbituril is added to form a supermolecule self-assembly body, and fluorescent materials with different fluorescence are prepared according to the difference of the added 2, 5-di (4-pyridine ethylene) toluene derivative and the difference of the added eight-membered cucurbituril.

2. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 1, which is characterized in that: the structural formula of the 2, 5-di (4-pyridine ethylene) toluene derivative is as follows:

wherein the R group has the formula CH₃、C₃H₇、C₅H₁₁Or C₇H₁₅。

3. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 1, which is characterized in that: the preparation method of the 2, 5-di (4-pyridine ethylene) toluene derivative comprises the following steps:

(1) adding 2, 5-dibromotoluene, 4-vinylpyridine, bis (triphenylphosphine) palladium dichloride and anhydrous potassium carbonate into DMF, mixing, and sealing the mixture in N₂Reacting for 18-32h at the temperature of 100-120 ℃ in a high-pressure reaction bottle under the atmosphere to obtain a product A;

(2) completely dissolving product A in dichloromethane to obtain black suspension to obtain product B;

(3) washing the product B with water and saturated saline solution sequentially to obtain product C;

(4) standing and layering the product C, separating the dichloromethane layer at the lowest layer, drying with anhydrous magnesium sulfate, spin-drying, and recrystallizing with ethanol to obtain pure 2, 5-di (4-pyridylethylene) toluene product;

(5) dissolving 2, 5-di (4-pyridine ethylene) toluene in DMF, adding 1-alkyl halide, reacting at 65-80 deg.C for 30-36h to obtain precipitate, cooling to room temperature, filtering, and washing the precipitate with petroleum ether, cyclohexane and acetone.

4. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 3, which is characterized in that: the 1-alkyl halide is methyl bromide, propyl bromide, pentane bromide or heptane bromide.

5. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 3, which is characterized in that: in the step (1), 0.5 to 1.5g of 2, 5-dibromotoluene, 1 to 1.5g of 4-vinylpyridine, 40 to 60mg of bistriphenylphosphine palladium dichloride and 1 to 1.5g of anhydrous potassium carbonate are added per 5mL of DMF.

6. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 5, which is characterized in that: 1g of 2, 5-dibromotoluene, 1.2g of 4-vinylpyridine, 50mg of bistriphenylphosphine palladium dichloride and 1.2g of anhydrous potassium carbonate were added per 5mL of the DMF.

7. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 3, which is characterized in that: in the step (3), the product B is washed for 3 times by water and saturated salt solution in sequence.

8. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 3, which is characterized in that: in the step (4), anhydrous ethanol is adopted for recrystallization.

9. The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain according to claim 3, which is characterized in that: the solvent DMF is an anhydrous solvent.

Technical Field

The invention relates to a preparation method of a supermolecule multicolor fluorescent material, in particular to a preparation method of a supermolecule multicolor fluorescent material regulated by an eight-membered cucurbituril and an alkyl chain.

Background

Fluorescent materials, especially white organic luminescent materials, have been widely used in the manufacture of large-screen transparent displays and the like. Energy transfer and exchange are the core of building the white organic light emitting material, but due to the existence of crosstalk, the improvement of the light energy transmission efficiency is still a bottleneck of the development of the white organic light emitting material. Therefore, the research for constructing multicolor fluorescent materials including white color is a research hotspot which is concerned by the theory and industry together. The traditional organic light-emitting material generally regulates the photophysical properties thereof through organic synthesis, but the method is time-consuming and labor-consuming and is not environment-friendly.

The supermolecule assembly can realize the regulation and control of the photophysical properties of the organic material by simply changing the interaction of host and guest among molecules, and is an effective way for realizing the preparation and regulation and control of the multicolor fluorescent material. However, at present, few studies on supramolecular multicolor fluorescent materials are available, and how to prepare fluorescent materials with different fluorescence by simple regulation and control methods is not reported at present.

Disclosure of Invention

The invention aims to provide a preparation method of an eight-membered cucurbituril and alkyl chain regulated supramolecular multicolor fluorescent material. The invention can prepare fluorescent materials with different colors by regulation and control, and has simple operation and easy production.

The technical scheme of the invention is as follows: a preparation method of an eight-membered cucurbituril and alkyl chain regulated supramolecular multicolor fluorescent material is characterized in that a fluorescent molecule 2, 5-di (4-pyridylethylene) toluene derivative is taken as a guest molecule, after the guest molecule is dissolved in water, a host molecule octal cucurbituril is added to form a supramolecular self-assembly body, and fluorescent materials with different fluorescence are prepared according to the difference of the added 2, 5-di (4-pyridylethylene) toluene derivative and the difference of the added octal cucurbituril.

In the preparation method of the eight-membered cucurbituril and alkyl chain-regulated supramolecular multicolor fluorescent material, the structural formula of the 2, 5-di (4-pyridylethylene) toluene derivative is shown in figure 1, wherein the molecular formula of the R group is CH₃、C₃H₇、C₅H₁₁Or C₇H₁₅。

In the preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain, the preparation method of the 2, 5-bis (4-pyridylethylene) toluene derivative comprises the following steps:

(1) adding 2, 5-dibromotoluene, 4-vinylpyridine, bis (triphenylphosphine) palladium dichloride and anhydrous potassium carbonate into DMF, mixing, and sealing the mixture in N₂Reacting for 18-32h at the temperature of 100-120 ℃ in a high-pressure reaction bottle under the atmosphere to obtain a product A;

(2) completely dissolving product A in dichloromethane to obtain black suspension to obtain product B;

(3) washing the product B with water and saturated saline solution sequentially to obtain product C;

(4) standing and layering the product C, separating the dichloromethane layer at the lowest layer, drying with anhydrous magnesium sulfate, spin-drying, and recrystallizing with ethanol to obtain pure 2, 5-di (4-pyridylethylene) toluene product;

(5) dissolving 2, 5-di (4-pyridine ethylene) toluene in DMF, adding 1-alkyl halide, reacting at 65-80 deg.C for 30-36h to obtain precipitate, cooling to room temperature, filtering, and washing the precipitate with petroleum ether, cyclohexane and acetone.

In the preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain, the 1-alkyl halide is methyl bromide, propyl bromide, pentane bromide or heptane bromide.

In the preparation method of the eight-membered cucurbituril and alkyl chain-regulated supramolecular multicolor fluorescent material, in the step (1), 0.5-1.5g of 2, 5-dibromotoluene, 1-1.5g of 4-vinylpyridine, 40-60mg of bis (triphenylphosphine) palladium dichloride and 1-1.5g of anhydrous potassium carbonate are added into every 5mL of DMF.

The preparation method of the eight-membered cucurbituril and alkyl chain-regulated supramolecular multicolor fluorescent material comprises the step of adding 1g of 2, 5-dibromotoluene, 1.2g of 4-vinylpyridine, 50mg of bis (triphenylphosphine) palladium dichloride and 1.2g of anhydrous potassium carbonate into every 5mL of DMF.

The preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain comprises the following steps: in the step (3), the product B is washed for 3 times by water and saturated salt solution in sequence.

In the preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain, in the step (4), the anhydrous ethanol is adopted for recrystallization.

In the preparation method of the supramolecular multicolor fluorescent material regulated by the eight-membered cucurbituril and the alkyl chain, the solvent DMF is an anhydrous solvent.

The invention has the advantages of

According to the invention, the 2, 5-di (4-pyridylethylene) toluene derivative is taken as a guest molecule, the eight-membered cucurbituril is taken as a host molecule, and the color of the fluorescent material can be regulated and controlled by adjusting the composition of the 2, 5-di (4-pyridylethylene) toluene derivative and the addition amount of the eight-membered cucurbituril, so that the multicolor fluorescent material is prepared. The method is simple and easy to produce, and has potential application value in the fields of biology, environment, energy and the like, such as fluorescent sensors, multicolor light-emitting diodes and the like.

To illustrate the advantageous effects of the present invention, the inventors made the following experiments:

first, the fluorescence of the supramolecular assembly is confirmed by a molar ratio method

PPV 1: the R group is CH₃2, 5-bis (4-pyridylethylene) toluene derivative of (a), PPV 2: r is C₃H₇2, 5-bis (4-pyridylethylene) toluene derivative of (a), PPV 3: r is C₅H₁₁2, 5-bis (4-pyridylethylene) toluene derivative of (a), PPV 4: r is C₇H₁₅And 2, 5-bis (4-pyridylethylene) toluene derivatives of (1).

In the concentration range of 10^-6～10^-4In mol/L guest molecule aqueous solution, when the excitation wavelength is 405nm, the maximum emission wavelength is 490nm, and when 0.5 times of eight-membered cucurbituril is gradually added into the guest molecule (PPV1-4) aqueous solution, the maximum emission wavelength of fluorescence is red shifted from 490nm to 550nm, which shows orange yellow fluorescence. After further addition of 0.5 times of eight-membered cucurbituril, the fluorescence emission intensity of the guest molecule (PPV1-4) gradually increased near the original position. When the octave cucurbituril is added to 2 times, the fluorescence of the PPV1-2 has no obvious change, the fluorescence of the PPV3 gradually generates red shift, the fluorescence shifts to 600nm and shows orange-red fluorescence, and the fluorescence shifts to 500nm and shows green fluorescence when the PPV4 is blue-shifted.

Secondly, confirming the assembly mode through nuclear magnetic spectrum

Dissolving the guest molecule in deuterated water, gradually dropwise adding the eight-membered cucurbituril into the deuterated water, and measuring a nuclear magnetic spectrum. Through analysis, PPV1-4 was confirmed to generate 2 specific stable assembly states and have corresponding fluorescence spectra for verification when 0.5-fold or 1-fold octave cucurbituril was added. When PPV3-4 is added with 2 times of eight-membered cucurbituril, a new assembly state appears and a corresponding fluorescence spectrum is obtained.

Drawings

FIG. 1 is a chemical structural formula of a guest molecule;

FIG. 2 is a fluorescence spectrum of PPV1 with eight-membered cucurbituril;

FIG. 3 is a fluorescence spectrum of PPV2 with eight-membered cucurbituril;

FIG. 4 is a fluorescence spectrum of PPV3 with the addition of eight-membered cucurbituril;

FIG. 5 shows the fluorescence spectrum of PPV4 with eight-membered cucurbituril.

FIG. 6 is a nuclear magnetic spectrum of PPV1 with eight-membered cucurbituril;

FIG. 7 is a nuclear magnetic spectrum of PPV2 with eight-membered cucurbituril;

FIG. 8 is a nuclear magnetic spectrum of PPV3 with the addition of eight-membered cucurbituril;

FIG. 9 is a nuclear magnetic spectrum of PPV4 with an eight-membered cucurbituril.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.

Examples of the invention