CN113979927B - Method for preparing fluorescent molecules through intermolecular self-assembly - Google Patents
Method for preparing fluorescent molecules through intermolecular self-assembly Download PDFInfo
- Publication number
- CN113979927B CN113979927B CN202111361420.9A CN202111361420A CN113979927B CN 113979927 B CN113979927 B CN 113979927B CN 202111361420 A CN202111361420 A CN 202111361420A CN 113979927 B CN113979927 B CN 113979927B
- Authority
- CN
- China
- Prior art keywords
- molecule
- reaction
- preparing
- ethyl acetate
- assembly according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention relates to a method for preparing fluorescent molecules through intermolecular self-assembly, and belongs to the field of functional materials. By using benzene rings and pyri-dines between molecules A and BPi-pi formation of the pyridine cation + And the function of the self-assembled accumulation among molecules is favorable for energy transfer and transition, so that a fluorescence signal is generated. Wherein the molecule A is a trivalent pyridinium ion structure prepared by taking 1,3, 5-tripyridyl benzene and 1-chlorobutane as raw materials; the molecule B is a monovalent pyridinium ion structure. The method has the advantages of high synthesis yield, mild reaction conditions, simple reaction steps, high fluorescence quantum yield and the like.
Description
Technical Field
The invention relates to a method for preparing fluorescent molecules through intermolecular self-assembly, and belongs to the field of functional materials.
Background
Fluorescence refers to a photoluminescence cold luminescence phenomenon. When a certain normal temperature substance is irradiated with incident light (usually ultraviolet light) of a certain wavelength, the light energy is absorbed and enters an excited state, and the excited state is immediately de-excited and emits emergent light (usually the wavelength is in the visible light band) longer than the wavelength of the incident light; many fluorescent substances immediately disappear upon stopping the incident light. One of the characteristics of fluorescent molecules is that the molecular structure requires a polycyclic aromatic hydrocarbon composition. It is difficult to generate fluorescence when there is no conjugated aromatic hydrocarbon in the molecule, which causes a limitation in preparing fluorescent molecules. In view of this problem, the present invention has developed a method for preparing fluorescent molecules by intermolecular self-assembly.
Disclosure of Invention
The invention aims to provide a method for preparing fluorescent molecules through intermolecular self-assembly, which utilizes pi-pi+ action formed by benzene rings and pyridine cations between two molecules to generate intermolecular self-assembly accumulation, thereby being beneficial to energy transfer and transition and generating fluorescent signals.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows: a method for preparing a fluorescent molecule by intermolecular self-assembly comprising the steps of: fluorescent molecules are generated by intermolecular self-assembly: at room temperature, equimolar molecules A and B are weighed and dissolved in ultrapure water, stirred and irradiated by an ultraviolet lamp to generate fluorescence.
The structural formulas of the molecule A and the molecule B are as follows:
further, the amounts of the molecular A and molecular B materials were 0.01mmol as equimolar amounts.
Further, the ultraviolet lamp wavelength was 356nm.
The preparation method of the molecule A comprises the following steps: the molecule A is prepared by taking 1,3, 5-tripyridyl benzene and 1-chlorobutane as raw materials.
Specifically, 1,3, 5-tripyridyl benzene and excessive 1-chlorobutane are dissolved in an organic solvent (preferably N, N-dimethylformamide), magnetically stirred, and heated to react (the reaction temperature is preferably 90 ℃), after the reaction is finished, the solution is cooled to room temperature, ethyl acetate is directly added, a large amount of yellow solid is separated out, the solution is filtered under reduced pressure, and unreacted 1,3, 5-tripyridyl benzene and 1-chlorobutane are simultaneously washed by ethyl acetate and removed, and then the solution is dried in vacuum to obtain a molecule A.
In order to ensure that one of the reactants 1,3, 5-tripyridylbenzene is able to react completely, the formation of monovalent pyridinium ions and monovalent pyridinium ions by-products is reduced, and further, the amount of 1-chlorobutane is 6-8 times that of 3, 5-diphenylpyridine.
Further, the magnetic stirring rotating speed is 160-200r/min.
In order to ensure that one of the reactants 1,3, 5-tripyridylbenzene can react completely, the generation of by-products monovalent pyridinium ions and monovalent pyridinium ions is reduced, and the reaction time is further 48-60h.
The preparation method of the molecule B comprises the following steps: (1) Dissolving 3, 5-diphenyl pyridine and excessive 1-chloro-2, 4-dinitrobenzene in an organic solvent (preferably N, N-dimethylformamide), magnetically stirring, heating to react (the reaction temperature is preferably 90 ℃), after the reaction is finished (generally reacting for 30 hours), cooling the solution to room temperature, directly adding ethyl acetate, precipitating and separating out a large amount of solid, decompressing and filtering, washing with ethyl acetate to remove unreacted 3, 5-diphenyl pyridine and 1-chloro-2, 4-dinitrobenzene, and drying in vacuum; (2) And dissolving the prepared sample and excessive aniline in an organic solvent (preferably N, N-dimethylformamide), magnetically stirring, heating to react (the reaction temperature is preferably 85 ℃), cooling the solution to room temperature after the reaction is finished (the reaction time is preferably 15 hours), directly adding ethyl acetate, precipitating a large amount of solids, carrying out vacuum suction filtration, washing with ethyl acetate to remove unreacted aniline, and carrying out vacuum drying to obtain the target molecule B.
In order to ensure that one of the reactants 3, 5-diphenylpyridine is able to react completely, further, the amount of 1-chloro-2, 4-dinitrobenzene material in step (1) is 2-3 times that of 3, 5-diphenylpyridine.
Further, the magnetic stirring rotating speed in the step (1) is 160-200r/min.
In order to increase the yield, the amount of aniline in step (1) is further the same as that of 1-chloro-2, 4-dinitrobenzene.
The beneficial effects of the invention are as follows: the method for preparing the fluorescent molecules through intermolecular self-assembly has the advantages of high synthesis yield, mild reaction conditions, simple reaction steps, high fluorescence quantum yield and the like.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
embodiment one:
the preparation of fluorescent molecules by intermolecular self-assembly comprises the following steps:
(1) Then, 309mg of 1,3, 5-tripyridyl benzene and 890mg of 1-chlorobutane were sequentially weighed and dissolved in 30mL of N, N-dimethylformamide, the mixture was magnetically stirred, the temperature of the solution was raised to 90 ℃, after 60 hours of reaction, the solution was cooled to room temperature, 60mL of ethyl acetate was directly added, a large amount of yellow solid was precipitated, the mixture was suction-filtered under reduced pressure, and at the same time, unreacted 1,3, 5-tripyridyl benzene and 1-chlorobutane were removed by washing with 60mL of ethyl acetate, and the mixture was dried under vacuum, and the solid was weighed to obtain 544mg. The hydrogen spectrum characterization data are as follows: ppm 9.21-9.20 (d, 6H), 8.92 (s, 3H), 8.86-8.84 (d, 6H), 4.77-4.74 (t, 6H), 2.14-2.08 (m, 6H), 1.54-1.48 (m, 6H), 1.09-1.06 (t, 9H).
(2) 231mg of 3, 5-diphenylpyridine and 404mg of 1-chloro-2, 4-dinitrobenzene are sequentially weighed and dissolved in 30mL of N, N-dimethylformamide, magnetic stirring is carried out, the temperature of the solution is raised to 90 ℃, after the reaction is carried out for 30 hours, the solution is cooled to room temperature, 60mL of ethyl acetate is directly added, a large amount of solid is separated out, the pressure is reduced, suction filtration is carried out, meanwhile, 40mL of ethyl acetate is used for washing and removing unreacted 3, 5-diphenylpyridine and 1-chloro-2, 4-dinitrobenzene, vacuum drying is carried out, and 289mg of solid is obtained after the solid is weighed; the prepared sample and 201mg of aniline are dissolved in 20mL of N, N-dimethylformamide, magnetic stirring is carried out, the temperature of the solution is raised to 85 ℃, after the reaction is carried out for 12 hours, the solution is cooled to room temperature, 100mL of ethyl acetate is directly added, a large amount of solids are separated out, vacuum filtration is carried out, meanwhile, 50mL of ethyl acetate is used for washing and removing unreacted aniline, vacuum drying is carried out, the target molecule is obtained, and the solid is weighed to obtain 135mg. The hydrogen spectrum characterization data are as follows: ppm 9.47-9.23 (m, 3H), 8.03-8.00 (m, 6H), 7.83-7.81 (m, 3H), 7.69-7.64 (m, 6H).
(3) At room temperature, 4.8mg and 3.4mg of each of the molecule A and the molecule B were weighed, dissolved in 10mL of ultrapure water, stirred, and irradiated with an ultraviolet lamp having a wavelength of 365nm to generate green fluorescence. The maximum emission peak of the fluorescent molecule is 556nm and the quantum yield is 27% through detection.
Embodiment two:
in the preparation of molecule A, the present invention uses the same preparation method as in step (1) of example one, but with different reactant ratios, the molar ratio between 1-chloro-2, 4-dinitrobenzene and 3, 5-diphenylpyridine is 1:1. the specific operation is as follows: 309mg of 1,3, 5-tripyridyl benzene and 411mg of 1-chlorobutane are sequentially weighed and dissolved in 30mL of N, N-dimethylformamide, magnetic stirring is carried out, the temperature of the solution is raised to 90 ℃, after the reaction is carried out for 60 hours, the solution is cooled to room temperature, 60mL of ethyl acetate is directly added, a large amount of yellow solid is separated out, vacuum suction filtration is carried out, meanwhile, the unreacted 1,3, 5-tripyridyl benzene and 1-chlorobutane are removed by washing with 60mL of ethyl acetate, vacuum drying is carried out, and the solid is weighed to obtain 397mg.
Embodiment III:
in the preparation of molecule B, the present invention uses the same preparation method as in step (2) of example one, but the reaction is carried out in different reactant ratios to prepare the reaction intermediate, the molar ratio between 1,3, 5-tripyridyl benzene and 1-chlorobutane is 1:3. the specific operation is as follows: 231mg of 3, 5-diphenylpyridine and 202mg of 1-chloro-2, 4-dinitrobenzene are sequentially weighed and dissolved in 30mL of N, N-dimethylformamide, magnetic stirring is carried out, the temperature of the solution is raised to 90 ℃, after the reaction is carried out for 30 hours, the solution is cooled to room temperature, 60mL of ethyl acetate is directly added, a large amount of solid is separated out, the pressure is reduced, suction filtration is carried out, meanwhile, the unreacted 3, 5-diphenylpyridine and 1-chloro-2, 4-dinitrobenzene are removed by washing with 40mL of ethyl acetate, vacuum drying is carried out, and the solid is weighed to obtain 201mg.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (9)
1. A method for preparing a fluorescent molecule by intermolecular self-assembly, characterized in that: the method comprises the following steps:
at room temperature, weighing equimolar molecules A and B, dissolving in ultrapure water, stirring, and irradiating by an ultraviolet lamp to generate fluorescence;
the structural formulas of the molecule A and the molecule B are shown as follows;
2. the method for preparing a fluorescent molecule by intermolecular self-assembly according to claim 1, wherein: the ultraviolet lamp wavelength was 356nm.
3. The method for preparing a fluorescent molecule by intermolecular self-assembly according to claim 1, wherein: the molecule A is prepared by the following method: the molecule A is prepared by taking 1,3, 5-tripyridyl benzene and 1-chlorobutane as raw materials.
4. A method for preparing a fluorescent molecule by intermolecular self assembly according to claim 3, wherein: the specific steps for preparing the molecule A are as follows: dissolving 1,3, 5-tripyridyl benzene and excessive 1-chlorobutane in an organic solvent, magnetically stirring, heating for reaction, cooling the solution to room temperature after the reaction is finished, directly adding ethyl acetate, precipitating a large amount of yellow solid, decompressing and filtering, washing with ethyl acetate to remove unreacted 1,3, 5-tripyridyl benzene and 1-chlorobutane, and drying in vacuum to obtain the product A.
5. The method for preparing a fluorescent molecule by intermolecular self-assembly according to claim 4, wherein: the organic solvent is N, N-dimethylformamide, and the reaction temperature is preferably 90 ℃.
6. The method for preparing a fluorescent molecule by intermolecular self-assembly according to claim 4, wherein: the amount of the 1-chlorobutane is 6-8 times that of 3, 5-diphenyl pyridine;
and/or the magnetic stirring rotating speed is 160-200r/min;
and/or the reaction time is 48-60h.
7. The method for preparing a fluorescent molecule by intermolecular self-assembly according to claim 1, wherein: the molecule B is prepared by the following method: (1) Dissolving 3, 5-diphenyl pyridine and excessive 1-chloro-2, 4-dinitrobenzene in an organic solvent, magnetically stirring, heating for reaction, cooling the solution to room temperature after the reaction is finished, directly adding ethyl acetate, precipitating a large amount of solid, decompressing and filtering, washing with ethyl acetate to remove unreacted 3, 5-diphenyl pyridine and 1-chloro-2, 4-dinitrobenzene, and vacuum drying; (2) And dissolving the prepared sample and excessive aniline in an organic solvent, magnetically stirring, heating for reaction, cooling the solution to room temperature after the reaction is finished, directly adding ethyl acetate, precipitating a large amount of solids, carrying out vacuum filtration, washing with ethyl acetate to remove unreacted aniline, and carrying out vacuum drying to obtain the target molecule B.
8. The method of preparing fluorescent molecules by intermolecular self-assembly according to claim 7, wherein: in the step (1), the organic solvent is N, N-dimethylformamide, the reaction temperature is 90 ℃, and the reaction is carried out for 30 hours;
and/or the organic solvent in the step (2) is N, N-dimethylformamide, the reaction is carried out at 85 ℃ for 15 hours.
9. The method of preparing fluorescent molecules by intermolecular self-assembly according to claim 7, wherein: the amount of the 1-chloro-2, 4-dinitrobenzene is 2-3 times that of the 3, 5-diphenylpyridine;
and/or the magnetic stirring rotating speed is 160-200r/min;
and/or the amount of the substance of aniline is the same as the amount of the substance of 1-chloro-2, 4-dinitrobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111361420.9A CN113979927B (en) | 2021-11-17 | 2021-11-17 | Method for preparing fluorescent molecules through intermolecular self-assembly |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111361420.9A CN113979927B (en) | 2021-11-17 | 2021-11-17 | Method for preparing fluorescent molecules through intermolecular self-assembly |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113979927A CN113979927A (en) | 2022-01-28 |
| CN113979927B true CN113979927B (en) | 2023-07-25 |
Family
ID=79749008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111361420.9A Active CN113979927B (en) | 2021-11-17 | 2021-11-17 | Method for preparing fluorescent molecules through intermolecular self-assembly |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113979927B (en) |
-
2021
- 2021-11-17 CN CN202111361420.9A patent/CN113979927B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113979927A (en) | 2022-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101321774A (en) | Process for preparing ortho-metallated metal compounds | |
| CN112300201B (en) | Synthesis and preparation method of trimeric indenyl coumarin-corrole-porphyrin quaternary system star-shaped compound | |
| CN111303010B (en) | Organic room-temperature phosphorescent material containing imide structure, preparation method and application thereof | |
| Maegawa et al. | Transparent and visible-light harvesting acridone-bridged mesostructured organosilica film | |
| CN113249116B (en) | Fluorescent organic-inorganic silicon oxide liquid crystal material and preparation method thereof | |
| CN108947766B (en) | Fluorine-containing tetraphenylethylene compound and preparation method and application thereof | |
| CN112442054B (en) | Preparation method of trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound | |
| CN111548431B (en) | Marine organism polysaccharide grafted pyridine organic micromolecule multicolor adjustable aggregation-induced emission material and preparation method thereof | |
| CN113979927B (en) | Method for preparing fluorescent molecules through intermolecular self-assembly | |
| CN112877064A (en) | Preparation method of pure Cs4PbBr6 perovskite quantum dot and product thereof | |
| CN111073638A (en) | Method for preparing controllable photoluminescence carbon dots by changing temperature | |
| CN115010763B (en) | Circular polarization phosphorescence platinum (II) complex, and preparation method and application thereof | |
| CN115960024A (en) | Cyanophenyl compounds with aggregation-induced delayed fluorescence characteristics and preparation method thereof | |
| CN115160588A (en) | Full-spectrum luminescent nanoscale zirconium-based metal organic framework material and preparation method thereof | |
| Cheng et al. | Synthesis and characterization of chiral polymer complexes incorporating polybinaphthyls, bipyridine, and Eu (III) | |
| CN108558595B (en) | P-phenylene ethylene bridged trimer indene derivative and preparation method thereof | |
| CN113461698A (en) | Trimeric indenyl dicumarol-corrole triplet photosensitizer and preparation method and application thereof | |
| CN117050331B (en) | Synthetic method of building column arene and terpyridine supermolecule crosslinked polymer | |
| CN111171059B (en) | Dehydroabietic acid and derivative-based europium ion fluorescent complex thereof and preparation method thereof | |
| CN115057883B (en) | Two-dimensional perovskite white light material and preparation method and application thereof | |
| CN116284008A (en) | Diimide photoluminescent material containing spin-inhibit system, and preparation method and application thereof | |
| CN110283193B (en) | Fluorescent probe compound with ground solid luminescent property and preparation method thereof | |
| CN110229055B (en) | Anthracene derivative with broad-spectrum upconversion white light emission characteristic and weak light upconversion white light system | |
| CN108570040B (en) | Barbituric acid compound of tetra-substituted thiophene and preparation method thereof | |
| CN117069741A (en) | Polymorphic luminescent type thermal activation delayed fluorescent molecule and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |