CN115504938A - Compound with photoinduced solid fluorescence change and preparation method thereof - Google Patents
Compound with photoinduced solid fluorescence change and preparation method thereof Download PDFInfo
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- 239000013067 intermediate product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
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- 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
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- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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Abstract
The invention discloses a compound with photoinduced solid fluorescence change, which has a structural general formula (1) and is prepared by the following steps: with (4- (1-phenyl-1H-benzo [ d ]]Imidazole-2-yl) phenyl) boric acid and 4-bromobenzene acetonitrile are used as initial raw materials, and a compound of a formula (1) is obtained through two-step reaction; the compound takes cyano stilbene as a core, and can change color after being illuminated under solid condition by connecting benzimidazole on one side of a conjugated system and connecting a flexible alkoxy group on the other side of the conjugated system.
Description
Technical Field
The invention relates to a fluorescent compound and a preparation method thereof, in particular to a compound with photoinduced solid fluorescence change and a preparation method thereof.
Background
Luminescent materials have received attention from researchers due to their wide application in the fields of optics, electronics, information storage, and bio-imaging. The light emitting behavior of conjugated molecules and polymers is usually performed in a solution state, but in practical applications they are usually present in a solid form (e.g., crystals, thin films, etc.). The luminescent molecules are usually present in the form of aggregates in the solid state, and the aggregation of the organic luminophores leads to partial or even complete luminescence quenching, which is called as aggregation quenching fluorescence (ACQ) effect, and this greatly limits the application range of the luminescent materials. With the increasing discovery of molecules with Aggregation Induced Emission (AIE) properties, solid-state light emitting materials such as tetraphenylethylene have received renewed attention. The movement (including intramolecular rotation and intramolecular vibration) of molecules of the type in an aggregation state is limited, so that non-radiative decay is inhibited, high fluorescence quantum efficiency is generated, strong fluorescence is emitted, and the problem that the luminescent material emits weak luminescence in a solid state is effectively solved. This unique property makes AIE-type luminescent materials ideal for practical solid-state light-emitting technology applications, and has been widely used in the fields of biological probes, organic light-emitting diodes, chemical sensors, and cellular imaging.
With the intensive research on AIE materials, more and more multifunctional and intelligent AIE materials have been developed, and among them, the optical stimulus responsive AIE materials are a very important class. Light is a non-contact method that minimizes damage to the material while achieving a stimulus response. In addition, the response intensity can be remotely and wirelessly controlled by the optical stimulation, and the response intensity can be directly controlled by changing the light intensity and the wavelength.
Because the molecules are regularly and orderly arranged in the solid state, the movement of the molecules is greatly limited and is not easy to be stimulated to respond, so that the material is difficult to carry out the fluorescent discoloration of the photoinduced solid. Most solid-state fluorescent color-changing molecules or polymers studied at this stage require extensive exposure to stimuli, such as pressure, fumigation, abrasion, which change the conformation of the molecule or molecule while causing irreversible damage to the material.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a compound with solid photochromism; the second purpose is to provide a preparation method of the compound.
The technical scheme is as follows: the chemical structural formula of the compound is as follows:
wherein R is H, F, cl, br or I; n is 2 to 5.
Preferably R is H.
The compound has a photochromic solid fluorescent function.
The preparation method of the compound comprises the following steps:
(1) Dissolving (4- (1-phenyl-1H-benzo [ d ] imidazole-2-yl) phenyl) boric acid and 4-bromobenzonitrile in a solvent, heating and reacting the solution under an alkaline environment by taking tetrakis (triphenylphosphine) palladium as a catalyst to obtain 2- (4 '- (1-phenyl-1H-benzo [ d ] imidazole-2-yl) - [1,1' -biphenyl ] -4-yl) acetonitrile (hereinafter referred to as intermediate 1) from yellow to dark brown;
(2) Dissolving the product obtained in the step (1) and p-hydroxybenzaldehyde in a solvent, and heating and reacting by taking piperidine as a catalyst to obtain (Z) -3- (4- (2- (2-ethoxyethoxy) ethoxy) phenyl) -2- (4 '- (1-phenyl-1H-benzo [ d ] imidazole-2-yl) - [1,1' -biphenyl ] -4-yl) acrylonitrile (hereinafter referred to as an intermediate product 2);
(3) Dissolving the product obtained in the step (2) and 2- (2-ethoxyethoxy) ethyl bromide or 1, 2-bis (2-bromoethoxy) ethane in a solvent, heating for reaction, and changing the solution from wine red to brown yellow to obtain a compound 3; the reaction equation is as follows:
r is H, F, cl, br or I; n is 2 to 5.
Preferably, the reaction temperature in the step (1) is 70-90 ℃, and the solvent is tetrahydrofuran; the reaction process TLC monitors the reaction progress, and the developing agent is ethyl acetate: petroleum ether = 1. Preferably, after the reaction in step (1) is finished, the method further comprises a purification process, wherein dichloromethane is firstly used for extraction, and then a mixture of ethyl acetate and petroleum ether is used as a mobile phase for column chromatography separation to obtain an intermediate product.
Preferably, the reaction temperature in the step (2) is 60-80 ℃, and the reaction solvent is a mixture of tetrahydrofuran and methanol; the reaction process TLC monitors the reaction progress, and the developing agent is ethyl acetate: dichloromethane = 1. Preferably, the purification process is further included after the reaction in step (2) is finished, the reaction solvent is firstly distilled off, dichloromethane is added for dissolution, then petroleum ether is added for precipitation, and finally the intermediate product is obtained by recrystallization of the mixture of dichloromethane and methanol.
Preferably, the reaction temperature in the step (3) is 70-120 ℃, and the reaction solvent is N, N-dimethylformamide; the reaction process TLC monitored the reaction progress, and the developing agent was ethyl acetate: dichloromethane = 1. Preferably, the purification process is also included after the reaction in the step (3) is finished, and dichloromethane is firstly adopted for extraction; then taking ethyl acetate and dichloromethane as mobile phases to carry out column chromatography separation, removing the solvent from the eluent, and dripping into petroleum ether to precipitate solids to obtain the product.
The invention mechanism is as follows: the fluorescent compound takes cyano stilbene as a core, has AIE property, can have strong luminescence property in a solid state, and is further enhanced in luminescence property by connecting a benzimidazole group on one side of a conjugated system; meanwhile, the other side of the molecule is connected with a flexible alkoxy group, and the repeated alkoxy group not only plays a role in promoting electron transfer, but also provides a certain free space for the solid photo-thermal effect, so that the limited molecule can move in a solid state, and further the photo-fluorescence change is realized.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable advantages: (1) The fluorescent compound takes cyano stilbene as a core, and can change color after being illuminated under the solid condition by connecting benzimidazole on one side of a conjugated system and connecting a flexible alkoxy group on the other side of the conjugated system; (2) The fluorescent compound realizes continuous change of three solid fluorescent colors under 365nm illumination, and has high contrast and identification degree; (3) The synthesis method synthesizes the final product through two steps, and the preparation method is simple and easy to operate; (4) Non-contact light is used as a stimulus source, so that damage and pollution to materials are reduced.
Description of the drawings:
FIG. 1 is a nuclear magnetic hydrogen spectrum of intermediate product 1 prepared in example 1;
FIG. 2 is a nuclear magnetic hydrogen spectrum of intermediate 2 prepared in example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the final product prepared in example 1;
FIG. 4 is a nuclear magnetic hydrogen spectrum of the final product prepared in example 2;
FIG. 5 is a fluorescent color change plot of a thin film of light-induced solid of the final product prepared in example 1;
FIG. 6 is a graph of the fluorescence spectra of the final product prepared in example 1 under 365nm UV light for various periods of time.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The compound with the photoinduced solid fluorescence change has the chemical structural formula as follows:
the preparation method comprises the following steps:
(1) Synthesis of 2- (4 '- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) - [1,1' -biphenyl ] -4-yl) acetonitrile (hereinafter referred to as intermediate 1)
A100 mL three-necked flask was charged with 3.2g (10 mmol) of (4- (1-phenyl-1H-benzo [ d ]]Imidazol-2-yl) phenyl) boronic acid, 2.6g (13 mmol) 4-bromobenzyl cyanide, 20mL at a concentration of 2mol/L K 2 CO 3 An aqueous solution, 30mL tetrahydrofuran and 0.18g (0.15 mmol) tetrakis (triphenylphosphine) palladium were heated to 70 ℃ under nitrogen and the reaction was stirred for 24h. TLC monitored the progress of the reaction during the reaction, and the developing solvent was ethyl acetate: petroleum ether = 1. After completion of the reaction, heating was stopped, the reaction mixture was cooled to room temperature, 100mL of water was added to the reaction mixture, the mixture was extracted three times with 100mL of dichloromethane, the organic phases were combined, washed with saturated brine, and dried by addition of anhydrous sodium sulfate.Removing the solvent by rotary evaporation, and separating the crude product by column chromatography, wherein the mobile phase is ethyl acetate and petroleum ether in a volume ratio of 1: and 5, mixing. The eluent was rotary evaporated to remove the solvent and dried under vacuum at 60 ℃ for 8 hours to give 3.2g of a white solid product, intermediate 1, in 82.8% yield.
Compound 1 was characterized using nuclear magnetism and the results are shown in FIG. 1, 1 H NMR(600MHz,DMSO),δ(ppm):7.81(d,1H),7.72(d,2H),7.68(d,2H),7.63–7.55(m,5H),7.49–7.45(m,2H),7.43(d,2H),7.34–7.27(m,2H),7.19(d,1H),4.08(s,2H)。
(2) Synthesis of (Z) -3- (4-hydroxyphenyl) -2- (4 '- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) - [1,1' -biphenyl ] -4-yl) acrylonitrile (hereinafter referred to as intermediate 2)
2.7g (7 mmol) of intermediate 1 and 1.7g (14 mmol) of p-hydroxybenzaldehyde were charged in a 100mL three-necked flask, and reacted at 70 ℃ for 36 hours with 30mL of tetrahydrofuran and 15mL of anhydrous methanol as a mixed solvent and 2mL of piperidine as a catalyst. TLC monitored the progress of the reaction during the reaction, and the developing solvent was ethyl acetate: dichloromethane = 1. After the reaction is finished, cooling the reaction liquid to room temperature, removing the solvent by rotary evaporation, then adding dichloromethane to dissolve the product, and then adding the mixed liquid into petroleum ether to separate out a precipitate. Filter and rinse the filter cake 3 times with 30mL dichloromethane. Adding dichloromethane and methanol into the crude product in a volume ratio of 2:1 to precipitate a yellow-green solid, and the yellow-green solid is dried in vacuum at 50 ℃ for 8 hours to obtain 2.6g of intermediate product 2 with a yield of 75.6%.
The intermediate product 2 was characterized by nuclear magnetism, and the results are shown in FIG. 2, 1 H NMR(600MHz,DMSO)δ(ppm):10.30(s,1H),7.99(s,1H),7.89(d,2H),7.82(dt,5H),7.77(d,2H),7.67–7.56(m,5H),7.50(d,2H),7.36–7.27(m,2H),7.20(d,1H),6.93(d,2H)。
(3) Synthesis of (Z) -3- (4- (2- (2-ethoxyethoxy) ethoxy) phenyl) -2- (4 '- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) - [1,1' -biphenyl ] -4-yl) acrylonitrile (hereinafter referred to as final product)
0.98g (2 mmol) of reactant 2,0.47g (2.4 mmol) of 2- (2-ethoxyethoxy) ethyl bromide, 1.38g (10 mmol) of K 2 CO 3 And 20mL of DMF was added to a 50mL three-necked flask under a nitrogen atmosphereStirred for 2h at 80 ℃. TLC monitored the progress of the reaction during the reaction, and the developing solvent was ethyl acetate: dichloromethane = 1. After the reaction is finished, the reaction solution is cooled to room temperature and poured into 200mL of water, then 100mL of dichloromethane is used for extraction for 4 times, organic phases are combined, and the solvent is removed by rotary evaporation to obtain a crude product. Separating the crude product by column chromatography, wherein the mobile phase is ethyl acetate and dichloromethane in a volume ratio of 1:25, and the eluent is rotated to evaporate part of the solvent, and then dropped into 100mL petroleum ether to slowly precipitate a light green solid, which is dried under vacuum at 60 ℃ for 8 hours to obtain 0.8g of the final product with a yield of 66.1%.
The final product was characterized by nuclear magnetism and the results are shown in FIG. 3, 1 H NMR(600MHz,DMSO)δ(ppm):8.04(s,1H),7.97(d,2H),7.86–7.80(m,5H),7.76(d,2H),7.65–7.57(m,5H),7.49(d,2H),7.31(dt,2H),7.19(d,1H),7.12(d,2H),4.20–4.17(m,2H),3.78–3.75(m,2H),3.60–3.57(m,2H),3.51–3.48(m,2H),3.43(q,2H),1.10(t,3H)。
example 2
The chemical structural formula of the fluorescent compound is as follows:
the preparation method comprises the following steps:
steps (1) and (2) were the same as in example 1;
(3) Synthesis of (Z) -3- (4- (2- (2- (2-bromoethoxy) ethoxy) phenyl) -2- (4 '- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) - [1,1' -biphenyl ] -4-yl) acrylonitrile (hereinafter referred to as the final product):
0.98g (2 mmol) of reactant 2,1.1g (4 mmol) of 1, 2-bis (2-bromoethoxy) ethane, 1.38g (10 mmol) of K 2 CO 3 And 20mL of DMF was added to a 50mL three-necked flask and stirred at 80 ℃ for 2h under nitrogen. TLC monitored the progress of the reaction during the reaction, and the developing solvent was ethyl acetate: dichloromethane = 1. After the reaction is finished, the reaction solution is cooled to room temperature and poured into 200mL of water, then 100mL of dichloromethane is used for extraction for 4 times, organic phases are combined, and the solvent is removed by rotary evaporation to obtain a crude product. Column layer of crude productSeparating by precipitation, wherein the mobile phase is ethyl acetate and dichloromethane in a volume ratio of 1:30, and the eluent is rotated to evaporate part of the solvent, and then dropped into 100mL petroleum ether to slowly precipitate a light green solid which is dried in vacuum at 60 ℃ for 8 hours to obtain 0.65g of the final product with a yield of 47.5%.
The final product was characterized by nuclear magnetism, and the results are shown in figure 4, 1 H NMR(600MHz,DMSO)δ(ppm):8.03(s,1H),7.97(d,2H),7.82(q,5H),7.75(d,2H),7.67–7.56(m,5H),7.49(d,2H),7.31(dt,2H),7.20(d,1H),7.12(d,2H),4.22–4.17(m,2H),3.81–3.77(m,2H),3.75(t,2H),3.64–3.56(m,6H)。
performance testing
1. The solid photochromic performance of the compound is tested by the following method:
(1) Compound 3 prepared in example 1 was added to dichloromethane to prepare a solution having a concentration of 10 mg/mL;
(2) Covering the hollowed patterns of the flowers on quartz glass, spraying the solution prepared in the step (1) on the quartz glass, and airing and curing;
(3) Covering a part of the pattern, and irradiating the uncovered area with 365nm ultraviolet light for 20min, wherein the fluorescence of the irradiated area is changed from green to blue; then, the irradiated and partially non-irradiated areas were covered, and then irradiated with 365nm ultraviolet light for 20min, at which time the fluorescence of the irradiated area changed to yellow, and a fluorescent pattern of three colors of blue, green, and yellow was formed, as shown in fig. 5.
2. Solid film fluorescence spectroscopy detection of fluorescent compounds
The fluorescent compound prepared in example 1 was dissolved in chloroform at a concentration of 20mg/mL, spin-coated on a 12 x 1mm quartz plate at 1000rpm, air-dried for curing, and then the quartz plate was placed in a fluorescence detector for testing. And irradiating the quartz plate with 365nm ultraviolet light for 5min and 30min, and respectively testing the fluorescence spectra. The results are shown in FIG. 6.
As can be seen from FIG. 6, in the initial state, the solid thin film exhibited green fluorescence, and the peak of the fluorescence intensity appeared around 470 nm. After 5min ultraviolet irradiation, the fluorescence color changes from green to blue, and the highest peak of the fluorescence intensity moves to near 450 nm. When the film was irradiated for 30min, the fluorescence color changed to yellow, and the peak also shifted to around 500 nm. The data show that the fluorescent color of the fluorescent molecule in the solid state can realize the conversion of three different colors of blue, green and yellow.
Claims (9)
1. A compound having a photoinduced solid fluorescence change, characterized by the chemical structural formula:
wherein R is H, F, cl, br or I; n is 2 to 5.
2. The compound of claim 1, wherein R is H or Br.
3. A process for the preparation of a compound according to claim 1, comprising the steps of:
(1) Dissolving (4- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) boric acid and 4-bromophenylacetonitrile in a solvent, heating and reacting under an alkaline environment by using tetrakis (triphenylphosphine) palladium as a catalyst to obtain a solution which is changed from yellow to dark brown to obtain 2- (4 '- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) - [1,1' -biphenyl ] -4-yl) acetonitrile;
(2) Dissolving the product obtained in the step (1) and p-hydroxybenzaldehyde in a solvent, heating and reacting by taking piperidine as a catalyst, and changing the yellow color of the solution into dark brown to obtain (Z) -3- (4- (2- (2-ethoxyethoxy) ethoxy) phenyl) -2- (4 '- (1-phenyl-1H-benzo [ d ] imidazole-2-yl) - [1,1' -biphenyl ] -4-yl) acrylonitrile;
(3) Reacting the product of the step (2) with Br-CH 2 -CH 2 -(CH 2 -CH 2 -O) n-1 -R is dissolved in a solvent, and the solution is heated to react, so that the solution is changed from wine red to brown yellow to obtain the compound; the synthetic route is as follows:
wherein R is H, F, cl, br or I; n is 2 to 5.
4. The method for preparing the compound according to claim 3, wherein the reaction temperature in step (1) is 70 to 90 ℃, and the solvent is tetrahydrofuran.
5. The method for preparing the compound according to claim 3, wherein the reaction temperature in the step (2) is 60 to 80 ℃, and the solvent is a mixture of tetrahydrofuran and methanol.
6. The method for preparing a compound according to claim 3, wherein the reaction temperature in the step (3) is 70 to 120 ℃ and the solvent is N, N-dimethylformamide.
7. The preparation method according to claim 3, wherein after the reaction in the step (1) is finished, the method further comprises a purification process of extracting with dichloromethane, and then performing column chromatography separation by using a mixture of ethyl acetate and petroleum ether as a mobile phase to obtain an intermediate product.
8. The preparation method according to claim 3, wherein the purification process is further included after the reaction in step (2) is completed, the reaction solvent is distilled off, dichloromethane is added to dissolve, petroleum ether is added to precipitate, and finally a mixture of dichloromethane and methanol is used for recrystallization to obtain the intermediate product.
9. The preparation method according to claim 3, wherein the reaction of step (3) is completed and then comprises a purification process, wherein dichloromethane is used for extraction; then taking ethyl acetate and dichloromethane as mobile phases to carry out column chromatography separation, removing the solvent from the eluent, and dripping into petroleum ether to precipitate solids to obtain the product.
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