CN115894521A - Fluorescent molecule based on cage-shaped oxacalixarene and preparation method and application thereof - Google Patents

Fluorescent molecule based on cage-shaped oxacalixarene and preparation method and application thereof Download PDF

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CN115894521A
CN115894521A CN202211267712.0A CN202211267712A CN115894521A CN 115894521 A CN115894521 A CN 115894521A CN 202211267712 A CN202211267712 A CN 202211267712A CN 115894521 A CN115894521 A CN 115894521A
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oxacalixarene
caged
fluorescent molecule
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陈志杰
史乐
王磊
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ZJU Hangzhou Global Scientific and Technological Innovation Center
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Abstract

The invention discloses a fluorescent molecule based on cagelike oxacalixarene and a preparation method and application thereof. The fluorescent molecule is cage-shaped oxacalixarene conjugated with a benzoate group or conjugated with a benzoic acid group as shown in the following formula (1):
Figure DDA0003893721760000011
wherein R is a benzoate group or a benzoic acid group. The invention takes phloroglucinol and 2,3,5, 6-tetrachloropyridine as raw materials to synthesize the chlorine substituted oxacalixarene with a cage structure, and takes the chlorine substituted oxacalixarene as a framework to introduce conjugated aryl groups, thereby designing and synthesizing a fluorescent molecule with a novel structureAt room temperature, the fluorescent molecules can emit purple or indigo fluorescence under the excitation of exciting light of 350-380 nm, and the fluorescence emission is obvious, thereby being convenient for detection. The fluorescent molecule has stable property, can be used for a long time, and the fluorescent property of the fluorescent molecule is easy to be regulated and controlled by a substituent.

Description

Fluorescent molecule based on cage-shaped oxacalixarene and preparation method and application thereof
Technical Field
The invention belongs to the field of photophysical science, and particularly relates to a fluorescent molecule based on cage-shaped oxacalixarene, a preparation method of the fluorescent molecule and application of the fluorescent molecule in a luminescent device.
Background
Fluorescent molecules have wide applications in the fields of chemistry, biology, materials and the like. Due to the characteristics of high sensitivity, visualization and the like, the fluorescent sensor plays an important role in the aspects of fluorescence sensing, biological imaging, display materials, optical devices and the like.
Compared with the metal complex fluorescent molecule, the organic fluorescent molecule has the characteristics of stable structure, solubility, reproducibility and the like, is suitable for large-scale preparation, and has wide application prospect. However, most organic fluorescent molecules lack effective bonding sites, so that the development of a fluorescent molecule recognition system is limited, and the actual application effect of fluorescent molecule sensing is reduced.
Calixarene is a macrocyclic compound with a special ring cavity structure, and has an inclusion capacity on neutral molecules and ions due to the fact that the calixarene has a hydrophobic pi cavity and a hydrophilic end surrounded by annular phenolic hydroxyl. More importantly, calixarene has a plurality of reactive sites, and derivatives containing various functional groups and having an adjustable pi cavity size can be prepared by simple chemical modification, and the derivatives are attracting attention in the fields of molecular recognition, substance detection and separation and the like.
With the intensive research on calixarene functionalization, the research on oxacalixarene is receiving more and more attention. For example, the patent with publication number CN107365291A discloses a synthesis method of oxacalix [4] arene single schiff base and its application in copper ion identification, and the patent with publication number CN103435603A discloses a coumarin-oxacalix [3] arene fluorescent reagent and its preparation and application in detecting ferric ions.
In particular, oxacalixarenes having a cage structure have potential as molecular devices due to their combination of the advantages of porous organic cages and calixarenes. In addition, the calixarene-based porous organic cages can serve as basic building blocks for the synthesis of supramolecular materials with emerging properties. Therefore, it is of great significance to develop novel oxacalixarene materials with cage-like structures and to study materials with new characteristics based on cage-like oxacalixarene.
Disclosure of Invention
Aiming at the bottleneck problems existing in the prior art, the invention provides a fluorescent molecule based on cage-shaped oxacalixarene, which has novel structure, reliable property and convenient and fast synthesis, a preparation method thereof and application thereof in a light-emitting device.
The invention firstly takes phloroglucinol and 2,3,5, 6-tetrachloropyridine as raw materials to synthesize the chlorine-substituted oxacalixarene with a cage-like structure under specific and appropriate conditions, and takes the chlorine-substituted oxacalixarene with the cage-like structure as a framework to introduce conjugated aryl groups, thereby designing and synthesizing the fluorescent molecule based on the cage-like oxacalixarene. At room temperature, the fluorescent molecule based on the cage-shaped oxacalixarene can emit purple or indigo fluorescence under the excitation of exciting light of 350-380 nm, and the fluorescence emission is obvious, so that the detection is convenient. The fluorescent molecule based on the cage-shaped oxacalixarene has stable property and can be used for a long time. In addition, the fluorescence property of the fluorescent molecule based on the cage-shaped oxacalixarene is easy to regulate and control through a substituent.
A caged oxacalixarene-based fluorescent molecule which is a caged oxacalixarene conjugated with a benzoate group or conjugated with a benzoic acid group as shown in the following formula (1):
Figure BDA0003893721740000021
in the formula (1), R is a substituent represented by the following formula (2) or (3):
Figure BDA0003893721740000022
at room temperature, the fluorescent molecules of the cage-shaped oxacalixarene conjugated with the methyl benzoate group can emit purple fluorescence under the excitation of exciting light of 350-380 nm; at room temperature, the fluorescent molecule of the cage-shaped oxacalixarene conjugated with benzoic acid group can emit indigo fluorescence under the excitation of exciting light of 350-380 nm. The fluorescent molecule based on the cage-shaped oxacalixarene has obvious fluorescence emission and is convenient to detect. The fluorescent molecule based on the cage-shaped oxacalixarene has stable property and can be used for a long time. And the fluorescence property of the fluorescent molecule based on the cage-shaped oxacalixarene is easy to regulate and control through a substituent.
The fluorescence emission mechanism of the fluorescent molecule based on the cage-shaped oxacalixarene provided by the invention is derived from the conjugation effect of a pyridine ring and a benzene ring on calixarene. Due to the electron-withdrawing effect of the carboxyl group, the caged oxacalixarene conjugated with a methyl benzoate group and the caged oxacalixarene conjugated with a benzoic acid group have different fluorescence emission wavelengths. Wherein the emission wavelength of the cage-shaped oxacalixarene conjugated with the benzoate group is 381nm and is in the wavelength range of purple light (380-420 nm), and the emission wavelength of the cage-shaped oxacalixarene conjugated with the benzoate group is 431nm and is in the wavelength range of indigo light (420-440 nm).
The invention also provides a preparation method of the fluorescent molecule based on the cage-shaped oxacalixarene, which comprises the preparation of cage-shaped oxacalixarene conjugated with methyl benzoate groups and the preparation of cage-shaped oxacalixarene conjugated with benzoic acid groups. The preparation method is simple to operate, reliable in route and low in cost.
A preparation method of a cage-shaped oxacalixarene-based fluorescent molecule comprises the following steps:
(1) Suspending phloroglucinol, 2,3,5, 6-tetrachloropyridine and cesium carbonate in degassed dimethyl sulfoxide solution, stirring and reacting at 110-130 ℃ for 11-18h under the protection of inert gas, washing after the reaction is finished, separating liquid, discarding an aqueous phase, spin-drying an organic phase, and recrystallizing the obtained solid to obtain chlorine-substituted cage-shaped oxacalixarene;
(2) Dissolving the chlorine-substituted caged oxacalixarene obtained in the step (1), 4-methoxycarbonylphenylboronic acid and a catalyst Pd SPhos GenIII in tetrahydrofuran, degassing the obtained solution, adding a degassed potassium phosphate aqueous solution under the protection of inert gas, heating the obtained mixed solution to 70-110 ℃ under the protection of inert gas, refluxing for not less than 12h, separating the solution after the reaction is finished, washing, discarding the aqueous phase, spin-drying the organic phase, suspending the obtained brownish black solid in dichloromethane, filtering the obtained suspension by using a diatomite pad, spin-drying the organic phase, suspending the obtained solid in ethanol, performing ultrasonic treatment for 25-60min, and filtering to obtain the caged oxacalixarene conjugated with methyl benzoate groups.
According to the preparation method of the fluorescent molecule based on the cage-shaped oxacalixarene, phloroglucinol and 2,3,5, 6-tetrachloropyridine are used as raw materials to synthesize the chlorine-substituted oxacalixarene with the cage-shaped structure under specific and appropriate conditions, and then the chlorine-substituted oxacalixarene with the cage-shaped structure is used as a framework, conjugated aryl groups are introduced, and the fluorescent molecule based on the cage-shaped oxacalixarene is designed and synthesized.
The invention creatively carries out coupling reaction on the chlorine-substituted oxacalixarene with the cage structure and aryl boric acid under the catalytic action of a catalyst Pd SPhos GenIII, and reflows under the alkaline environment provided by potassium phosphate aqueous solution to obtain the cage oxacalixarene conjugated with methyl benzoate groups.
In addition, in the preparation method of the invention, the step (2) comprises a process of suspending the obtained brownish black solid in dichloromethane and then filtering the obtained suspension by using a diatomite pad, and a process of suspending the solid obtained after the organic phase is dried in a spinning way in ethanol and carrying out ultrasonic treatment, thereby realizing the removal of impurities generated in the reaction process and improving the purity of the target substance.
Preferably, in the step (1), the molar ratio of the phloroglucinol, the 2,3,5, 6-tetrachloropyridine and the cesium carbonate is 1 (1.2-1.8) to (3.0-4.0).
Preferably, in step (1), the organic phase obtained by discarding the aqueous phase is washed with a saturated saline solution several times to remove the dimethylsulfoxide solvent in the organic phase as much as possible to facilitate the spin-drying of the organic phase.
Preferably, in step (1), the solid obtained by spin-drying the organic phase is recrystallized using acetone. The acetone recrystallization method facilitates the reaction and avoids the use of a large amount of organic solvents in column chromatography operation.
Preferably, in the step (2), the molar ratio of the chlorine-substituted caged oxacalixarene to the 4-methoxycarbonylphenylboronic acid is 1 (6-7). More preferably, the molar ratio of the chlorine-substituted caged oxacalixarene to the 4-methoxycarbonylphenylboronic acid is 1 (6.3-6.8), and the proper excess of the 4-methoxycarbonylphenylboronic acid is in the range of the molar ratio, so that the six methyl benzoate-substituted caged oxacalixarene can be prepared.
A preparation method of a fluorescent molecule based on cage-shaped oxacalixarene comprises the following steps:
dissolving the cage-shaped oxacalixarene conjugated with methyl benzoate group in a 1, 4-dioxane aqueous solution, adding a potassium hydroxide aqueous solution, heating and refluxing the obtained mixed solution at 105-115 ℃ for not less than 24h, after the reaction is finished, spin-drying the solution, dissolving the remainder in water, slowly dropwise adding concentrated hydrochloric acid until the pH value is less than 3, filtering the generated precipitate, washing and drying to obtain the cage-shaped oxacalixarene conjugated with benzoic acid group.
The cage-shaped oxacalixarene conjugated with methyl benzoate groups provided by the invention can be further prepared into the cage-shaped oxacalixarene conjugated with benzoic acid groups through ester group hydrolysis reaction. Due to the electron-withdrawing effect of the carboxyl group, the two fluorescent molecules have different fluorescent properties, and the fluorescent property based on the cage-shaped oxacalixarene provided by the invention is easy to regulate and control through a substituent.
Preferably, the concentration of the potassium hydroxide aqueous solution is 1mol/L.
Preferably, the volume ratio of the 1, 4-dioxane to the deionized water is 1.
The invention also provides application of the fluorescent molecule based on the cage-shaped oxacalixarene in a light-emitting device.
Compared with the prior art, the invention has at least the following advantages:
1. the invention creatively synthesizes the fluorescent molecule based on the cage-shaped oxacalixarene with a novel structure, and further enriches the types of calixarene. Particularly, the invention creatively carries out coupling reaction on the chlorine-substituted oxacalixarene with the cage-like structure and aryl boric acid under the catalytic action of a catalyst Pd SPhos GenIII, introduces a conjugated aryl group, and designs and synthesizes a fluorescent molecule based on the cage-like oxacalixarene based on the conjugated effect of a pyridine ring and a benzene ring on calixarene.
2. The fluorescent molecule based on the cagelike oxacalixarene provided by the invention has fluorescence property due to the conjugated effect of the pyridine ring and the benzene ring on the calixarene, can emit purple or indigo fluorescence under the excitation of exciting light of 350-380 nm at room temperature, has obvious fluorescence emission and is convenient to detect.
3. The fluorescent molecule based on the cage-shaped oxacalixarene provided by the invention has stable property and can be used for a long time.
4. The fluorescence property based on the cage-shaped oxacalixarene provided by the invention is easy to regulate and control through a substituent.
5. The preparation method based on the cage-shaped oxacalixarene fluorescent molecule provided by the invention is simple to operate, reliable in route and low in cost.
6. The cage-shaped oxacalixarene-based organic composite material provided by the invention can combine the advantages of a porous organic cage and calixarene, and provides a new building element for exploring and synthesizing functionalized organic compounds, supramolecular compounds and metal complexes.
Drawings
FIG. 1 shows the content of Cage-6Me measured in example 4 3 Experimental data result chart of fluorescence emission spectrum and excitation spectrum of (1);
FIG. 2 is a graph showing the results of experimental data on fluorescence emission spectra and excitation spectra of Cage-6c measured in example 4;
FIG. 3 shows Cage-6Me obtained in example 4 3 And the CIE chromaticity diagram of Cage-6 c.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
The synthesis method of the chlorine substituted cage-shaped oxacalixarene comprises the following steps:
Figure BDA0003893721740000061
phloroglucinol (4.1 g) was weighed in a 500mL round-bottomed flask, and 10.6g of 2,3,5, 6-tetrachloropyridine, 37g of cesium carbonate and 200mL of dimethyl sulfoxide were sequentially added thereto, followed by stirring reaction at 120 ℃ for 12 hours under a nitrogen atmosphere. After the reaction was completed, 250mL of methylene chloride and 200mL of water were sequentially added and washed. The aqueous phase was further washed with 2X 200mL of dichloromethane. And washing the combined organic phase with 2X 200mL of saturated common salt, discarding the water phase, drying the organic phase for 10min by using anhydrous sodium sulfate, filtering, spin-drying the solvent, suspending the residue in 200mL of acetone for recrystallization, performing ultrasonic treatment for 10min, filtering, and washing with 100mL of acetone for three times to obtain a solid, namely the chlorine-substituted caged oxacalixarene Cage-6Cl (2.8-3.8 g, the yield is 25.3% -34.3%).
The product prepared in this example had the following characterization data:
chlorine substituted caged oxacalixarene Cage-6Cl
1 H NMR(600MHz,CDCl 3 ):δ7.77(s,3H),6.56(s,6H).
Example 2
Cage-like oxacalixarenes Cage-6Me conjugated with methyl benzoate 3 The synthesis method comprises the following steps:
Figure BDA0003893721740000071
1.2g of the chloro-substituted caged oxacalixarene prepared in example 1 was weighed in a 250mL round-bottomed flask, 2.16g of 4-methoxycarbonylphenylboronic acid, 0.3g of the catalyst Pd SPhos GenIII and 120mL of tetrahydrofuran were added in this order, and the suspension was degassed for 1 hour. Further, 30mL of 1mol/L potassium phosphate solution which had been subjected to deaeration treatment was added. The system is refluxed for 12 hours at 80 ℃ under the protection of nitrogen atmosphere. After the reaction was complete, the solution was cooled to room temperature, the aqueous phase was removed and the organic phase was spin dried under vacuum. The residue was dissolved in 200mL of dichloromethane, dried by adding anhydrous sodium sulfate, and the solution was filtered through a pad of celite. Spin-drying the obtained gray yellow solution, adding 100mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min to obtain a gray yellow solid, namely the Cage-shaped oxacalixarene Cage-6Me conjugated with the methyl benzoate group 3 (1.35 g, 59% yield).
The product prepared in this example has the following characterization data:
caged oxacalixarenes Cage-6Me conjugated with methyl benzoate groups 3
1 H NMR(600MHz,CDCl 3 ,298K)δ(ppm):8.11(d,12H),7.90(s,3H),7.74(d,12H),6.67(s,6H),3.94(s,18H). 13 CNMR(600MHz,CDCl 3 ,298K)δ(ppm):171.20,166.90,158.81,154.90,143.11,139.97,129.92,129.45,129.00,117.20,115.66,60.49,52.28.HRMS:m/z calcd for(M+H) + [C 75 H 52 N 3 O 18 ] + :1282.24,found:1282.435
Example 3
The synthesis method of the caged oxacalixarene Cage-6c conjugated with benzoic acid comprises the following steps:
Figure BDA0003893721740000081
cage-shaped oxacalixarene Cage-6Me substituted by methyl benzoate prepared in example 2 was weighed 3 0.4g was placed in a 250mL round bottom flask, and 20mL1, 4-dioxane and 80mL of an aqueous solution containing 4.48g of potassium hydroxide were added. The resulting mixed solution was refluxed at 110 ℃ for 24 hours. After the reaction is finished, spin-drying the solvent to obtain the residueThe material was dissolved in 100mL of water and concentrated hydrochloric acid was gradually added dropwise to a solution pH =2. Filtering, collecting white precipitate to obtain Cage-shaped oxacalixarene Cage-6c (0.33g, 91.6%)
The characterization data of the caged oxacalixarene conjugated with benzoic acid group, cage-6c, prepared in this example are as follows:
1 H NMR(600MHz,DMSO-d6,298K)δ(ppm):12.99(s,6H),8.15(s,3H),8.01(d,J=8.19Hz,12H),7.94(d,J=8.16Hz,12H),6.96(s,6H), 13 CNMR(600MHz,DMSO-d6,298K)δ(ppm):167.54,158.60,154.84,139.78,130.18,129.74,117.01,116.01,66.86.
example 4
Caged oxacalixarenes Cage-6Me conjugated with methyl benzoate groups 3 And fluorescence performance of caged oxacalixarene conjugated with benzoic acid group, cage-6 c.
The method specifically comprises the following steps:
(a) The Cage-6Me synthesized in example 2 and example 3 3 And Cage-6c in a vacuum oven heated to 120 deg.C and dried in vacuum for 24h to remove residual solvent molecules.
(b) Placing 50mg of the solid powder obtained in step (a) in a quartz plate, and measuring an emission spectrum and an excitation spectrum.
The results are shown in FIGS. 1 and 2, and FIG. 3 shows the obtained Cage-6Me 3 And the CIE chromaticity diagram of Cage-6 c. According to the analysis of the experimental results, the following results are obtained: caged oxacalixarenes Cage-6Me conjugated with a benzoate group 3 And caged oxacalixarene conjugated with a benzoic acid group, cage-6c, have fluorescence emission properties. Wherein, cage-6Me 3 The fluorescence emission peak wavelength of the fluorescent material reaches 381nm under the excitation of 354nm excitation light, and the fluorescence emission peak wavelength of the fluorescent material reaches 431nm under the excitation of 376nm excitation light by Cage-6 c. Cage-6Me 3 And Cage-6c have different emission wavelengths, which indicates that the fluorescent property can be controlled by the substituent group.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. A fluorescent molecule based on caged oxacalixarene, characterized in that the fluorescent molecule based on caged oxacalixarene is a caged oxacalixarene conjugated with a benzoate group or conjugated with a benzoic acid group as shown in the following formula (1):
Figure FDA0003893721730000011
in the formula (1), R is a substituent represented by the following formula (2) or (3):
Figure FDA0003893721730000012
at room temperature, the fluorescent molecules of the cage-shaped oxacalixarene conjugated with the methyl benzoate group can emit purple fluorescence under the excitation of exciting light of 350-380 nm;
at room temperature, the fluorescent molecule of the cage-shaped oxacalixarene conjugated with benzoic acid group can emit indigo fluorescence under the excitation of exciting light of 350-380 nm.
2. The method for preparing a caged oxacalixarene-based fluorescent molecule according to claim 1, wherein the method for preparing a caged oxacalixarene conjugated with a benzoate group comprises the following steps:
(1) Suspending phloroglucinol, 2,3,5, 6-tetrachloropyridine and cesium carbonate in degassed dimethyl sulfoxide solution, stirring and reacting at 110-130 ℃ for 11-18h under the protection of inert gas, washing after the reaction is finished, separating liquid, discarding an aqueous phase, spin-drying an organic phase, and recrystallizing the obtained solid to obtain chlorine-substituted cage-shaped oxacalixarene;
(2) Dissolving the chlorine-substituted caged oxacalixarene obtained in the step (1), 4-methoxycarbonylphenylboronic acid and a catalyst Pd SPhos GenIII in tetrahydrofuran, degassing the obtained solution, adding a degassed potassium phosphate aqueous solution under the protection of inert gas, heating the obtained mixed solution to 70-110 ℃ under the protection of inert gas, refluxing for not less than 12h, separating, washing, discarding the aqueous phase after the reaction is finished, spin-drying the organic phase, suspending the obtained brownish black solid in dichloromethane, filtering the obtained suspension by using a diatomite pad, spin-drying the organic phase, suspending the obtained solid in ethanol, performing ultrasonic treatment for 25-60min, and filtering to obtain the caged oxacalixarene conjugated with methyl benzoate groups.
3. A method for preparing a caged oxacalixarene-based fluorescent molecule as claimed in claim 2 wherein, in step (1), the molar ratio of phloroglucinol, 2,3,5, 6-tetrachloropyridine and cesium carbonate is 1 (1.2-1.8) to (3.0-4.0).
4. The method for preparing a caged oxacalixarene-based fluorescent molecule according to claim 2 wherein in step (1), the organic phase from which the aqueous phase is discarded is washed a plurality of times with saturated brine.
5. The method for preparing a caged oxacalixarene-based fluorescent molecule as claimed in claim 2, wherein in step (1), the solid obtained by spin drying the organic phase is recrystallized using acetone.
6. The method for preparing a caged oxacalixarene-based fluorescent molecule according to claim 2, wherein in the step (2), the molar ratio of the chlorine-substituted caged oxacalixarene to the 4-methoxycarbonylphenylboronic acid is 1 (6-7).
7. The method for preparing a caged oxacalixarene-based fluorescent molecule according to claim 1, wherein the method for preparing a caged oxacalixarene conjugated with a benzoic acid group comprises the following steps:
dissolving the cage-shaped oxacalixarene conjugated with methyl benzoate group in a 1, 4-dioxane aqueous solution, adding a potassium hydroxide aqueous solution, heating and refluxing the obtained mixed solution at 105-115 ℃ for not less than 24h, after the reaction is finished, spin-drying the solution, dissolving the remainder in water, slowly dropwise adding concentrated hydrochloric acid until the pH value is less than 3, filtering the generated precipitate, washing and drying to obtain the cage-shaped oxacalixarene conjugated with benzoic acid group.
8. The method of claim 7, wherein the concentration of the aqueous solution of potassium hydroxide is 1mol/L.
9. The method for preparing a caged oxacalixarene-based fluorescent molecule according to claim 7 wherein in the 1, 4-dioxane aqueous solution, the volume ratio of 1, 4-dioxane to deionized water is 1.
10. Use of the caged oxacalixarene-based fluorescent molecule according to claim 1 in a light emitting device.
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