CN114478559B - Solid-state light-stimulated fluorescence rapid color-changing material, and preparation method and application thereof - Google Patents
Solid-state light-stimulated fluorescence rapid color-changing material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114478559B CN114478559B CN202210213790.6A CN202210213790A CN114478559B CN 114478559 B CN114478559 B CN 114478559B CN 202210213790 A CN202210213790 A CN 202210213790A CN 114478559 B CN114478559 B CN 114478559B
- Authority
- CN
- China
- Prior art keywords
- solid
- condensation reaction
- dehydration condensation
- state light
- preparation
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent 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
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides a solid-state light-stimulated fluorescence rapid color-changing material, and a preparation method and application thereof, and belongs to the technical field of photochromic materials. The molecular structure of the invention is a series of solid state photochromic materials with different ester chain lengths and different flexible chain types, which are synthesized by dehydration reaction by taking spiropyran as a basic structural unit. The solid state ultraviolet lamp can show distinct dual color changes of ultraviolet-visible absorption spectrum and fluorescence emission spectrum before and after irradiation by 365nm ultraviolet lamp. After short-time irradiation of 524nm green light, the ultraviolet-visible absorption spectrum and the fluorescence emission spectrum of the material can be quickly and reversibly restored to the original colors and states, and the material has excellent fatigue resistance, high response and reversibility.
Description
Technical Field
The invention relates to the technical field of photochromic materials, in particular to a solid-state light-stimulated fluorescence rapid-color-changing material, and a preparation method and application thereof.
Background
A photochromic material refers to a specific material, the color and fluorescence emission of which are obviously changed under the alternate irradiation of specific light waves. Spiropyran (SP) molecules, as photochromic molecules that have been widely reported, can undergo a colorless-purple color transition under irradiation of ultraviolet light and a change in fluorescence emission without fluorescence-red fluorescence. Based on the excellent color-changing property, the SP has great potential application value in the fields of photoelectric devices, anti-counterfeiting coatings and the like. However, the SP molecules reported earlier can only realize the photochromic property by being dissolved in an organic solvent, and cannot realize the photochromic property due to close accumulation between molecules in a solid state, so that the practical application scene of the SP is limited.
Chinese patent CN110627800a discloses a solid state photochromic material based on a combination of SP and twisted aggregation-induced emission (AIE) materials, which has reversible color change and bifluorescence switching optical properties under alternating stimulus of ultraviolet light and visible light at 365 nm. But the reversible recovery process of the material requires several hours of visible light stimulus to be able to achieve.
Disclosure of Invention
In view of the above, the invention aims to provide a solid-state light-stimulated fluorescence rapid color-changing material, and a preparation method and application thereof. The solid state light stimulated fluorescence rapid color change material prepared by the invention has excellent reversibility and rapid response property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a solid-state light-stimulated fluorescence rapid color-changing material, which has a structure shown in a formula I:
wherein Ar is-C 5 H 9 O 2 、-C 6 H 11 O 2 、-C 7 H 13 O 2 、-C 8 H 15 O 2 、-C 5 H 10 NO or-C 6 H 13 。
Preferably, the solid-state light-stimulated fluorescence rapid-coloring material has a structure shown in formulas 1 to 6:
the invention also provides a preparation method of the solid-state light-stimulated fluorescence rapid color-changing material, which comprises the following steps:
when Ar is-C 5 H 9 O 2 、-C 6 H 11 O 2 、-C 7 H 13 O 2 or-C 8 H 15 O 2 When in use, the preparation method comprises the following steps:
mixing alkyl alcohol, 1-carboxyethyl indoline spiropyran, 4-lutidine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide for a first dehydration condensation reaction to obtain the solid state light stimulated fluorescence rapid color change material; the alkyl alcohol is ethanol, propanol, butanol or amyl alcohol;
when Ar is-C 5 H 10 In the NO state, the preparation method comprises the following steps of:
mixing an organic solvent, ethylamine, 1-carboxyethyl indoline spiropyran, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1-hydroxybenzotriazole to perform a second dehydration condensation reaction, so as to obtain the solid light-stimulated fluorescence rapid color-changing material;
when Ar is-C 6 H 13 When in use, the preparation method comprises the following steps:
mixing an organic solvent, 2, 3-trimethyl-3H-indole and bromohexane, and performing a first reflux reaction to obtain a first reflux product;
and mixing the first reflux product, the organic solvent and the 5-nitro salicylaldehyde, and performing a second reflux reaction to obtain the solid-state light-stimulated fluorescence rapid color-changing material.
Preferably, the molar ratio of the 1-carboxyethylindoline spiropyran, the alkyl alcohol, the 4-lutidine and the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1: 322-592: 0.3:1.9.
preferably, the molar ratio of the 1-carboxyethylindoline spiropyran, ethylamine, 1-hydroxybenzotriazole to 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:1.5:2:2.
preferably, the temperature of the first dehydration condensation reaction and the second dehydration condensation reaction are both 25 ℃ and the time is 24 hours.
Preferably, the first dehydration condensation reaction and the second dehydration condensation reaction further comprise post-treatment, and the post-treatment process is to sequentially carry out suction filtration, reduced pressure distillation and silica gel column separation and purification on the obtained dehydration condensation reaction product.
Preferably, the molar ratio of the 2, 3-trimethyl-3H-indole, bromohexane and 5-nitrosalicylaldehyde is 10:9.6:9.
preferably, the time of the first reflux reaction is 24 hours, and the time of the second reflux reaction is 20 hours.
The invention also provides application of the solid-state light-stimulated fluorescence rapid color-changing material in the fields of reversible fluorescence color change and rapid color switching.
The invention provides a solid state light stimulated fluorescence rapid color-changing material, the specific molecular structure is a series of solid state light stimulated fluorescence color-changing materials with different ester chain lengths and different flexible chain types which are synthesized by dehydration reaction by taking Spiropyran (SP) as a basic structural unit, the material provided by the invention can show obvious double spectral changes of visible light color and dark environment red fluorescence before and after irradiation by an ultraviolet lamp with 365nm under the powder state, and after short irradiation by green visible light with 524nm, the visible light color and dark environment red fluorescence caused by irradiation by the ultraviolet lamp can be rapidly and reversibly restored to the original color and state, thereby having excellent reversibility and rapid response property, and having great potential application value in the fields of anti-counterfeiting, super-resolution imaging and the like.
The data of the embodiment show that after the solid powder of the solid light-stimulated fluorescence rapid-color-changing material provided by the invention is irradiated by a 365nm ultraviolet lamp, the ultraviolet-visible absorption spectrum and the fluorescence emission spectrum are obviously changed, and after the solid powder is continuously irradiated by 524nm lamplight for 10 minutes, all the spectrums can be rapidly and reversibly changed into a state not irradiated by the ultraviolet lamp, and the reversible change of the light stimulation can be repeated for more than 500 times.
The invention also provides a preparation method of the solid state light stimulated fluorescence rapid color change material, which has the advantages of low raw material cost and simple synthetic route.
Drawings
FIG. 1 shows the change of powder color and dark ambient powder fluorescence color of the photochromic material prepared in example 1 in a powder state under sunlight before and after alternating irradiation of 365nm ultraviolet lamp and 524nm green lamp;
FIG. 2 is a graph showing the change of powder color and dark ambient powder fluorescent color of the photochromic material prepared in example 2 in a powder state under sunlight before and after alternating irradiation of 365nm ultraviolet lamp and 524nm green lamp;
FIG. 3 shows the change of powder color and dark ambient powder fluorescence color of the photochromic material prepared in example 3 in a powder state under sunlight before and after alternating irradiation of 365nm ultraviolet lamp and 524nm green lamp;
FIG. 4 shows the change of powder color and dark ambient powder fluorescence color of the photochromic material prepared in example 4 in powder state under sunlight before and after alternating irradiation of 365nm ultraviolet lamp and 524nm green lamp;
FIG. 5 shows the change of powder color and dark ambient powder fluorescence color of the photochromic material prepared in example 5 in powder state under sunlight before and after alternating irradiation of 365nm ultraviolet lamp and 524nm green lamp;
FIG. 6 shows the change of powder color and dark ambient powder fluorescence color of the photochromic material prepared in example 6 in powder state under sunlight before and after alternating irradiation of 365nm ultraviolet lamp and 524nm green lamp;
FIG. 7 is a graph showing the change in the ultraviolet-visible absorption spectrum and fluorescence spectrum of the solid powder of example 1 before and after irradiation with 365nm ultraviolet lamp;
FIG. 8 is a graph showing the variation of the UV-visible absorption spectrum and the fluorescence spectrum of the solid powder of example 1 alternately irradiated by a 365nm UV lamp and a 524nm green lamp at different time scales.
In FIG. 9 a) and b) are the two-molecule structure distributions of the synthetic monomer 1-carboxyethylindoline spiropyran single crystal (SP-COOH) and the single crystal of example 3, respectively, and c) and d) are the parallelogram structure distributions formed by the four molecules in one unit cell of SP-COOH and example 3, respectively.
Detailed Description
The invention provides a solid-state light-stimulated fluorescence rapid color-changing material, which has a structure shown in a formula I:
wherein Ar is-C 5 H 9 O 2 、-C 6 H 11 O 2 、-C 7 H 13 O 2 、-C 8 H 15 O 2 、-C 5 H 10 NO or-C 6 H 13 。
In the invention, the solid-state light-stimulated fluorescence rapid color-changing material has a structure shown in formulas 1-6:
the invention also provides a preparation method of the solid-state light-stimulated fluorescence rapid color-changing material, which comprises the following steps:
when Ar is-C 5 H 9 O 2 、-C 6 H 11 O 2 、-C 7 H 13 O 2 or-C 8 H 15 O 2 When in use, the preparation method comprises the following steps:
mixing alkyl alcohol, 1-carboxyethyl indoline spiropyran, 4-lutidine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide for a first dehydration condensation reaction to obtain the solid state light stimulated fluorescence rapid color change material; the alkyl alcohol is ethanol, propanol, butanol or amyl alcohol;
when Ar is-C 5 H 10 In the NO state, the preparation method comprises the following steps of:
mixing an organic solvent, ethylamine, 1-carboxyethyl indoline spiropyran, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1-hydroxybenzotriazole to perform a second dehydration condensation reaction, so as to obtain the solid light-stimulated fluorescence rapid color-changing material;
when Ar is-C 6 H 13 When in use, the preparation method comprises the following steps:
mixing an organic solvent, 2, 3-trimethyl-3H-indole and bromohexane, and performing a first reflux reaction to obtain a first reflux product;
and mixing the first reflux product, the organic solvent and the 5-nitro salicylaldehyde, and performing a second reflux reaction to obtain the solid-state light-stimulated fluorescence rapid color-changing material.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
When Ar is-C 5 H 9 O 2 、-C 6 H 11 O 2 、-C 7 H 13 O 2 or-C 8 H 15 O 2 In the time-course of which the first and second contact surfaces,the preparation method comprises the following steps:
mixing alkyl alcohol, 1-carboxyethyl indoline spiropyran, 4-lutidine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide for a first dehydration condensation reaction to obtain the solid state light stimulated fluorescence rapid color change material; the alkyl alcohol is ethanol, propanol, butanol or amyl alcohol.
In the present invention, the molar ratio of the 1-carboxyethylindoline spiropyran, the alkyl alcohol, the 4-lutidine to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is preferably 1: 322-592: 0.3:1.9.
in the present invention, the temperature of the first dehydration condensation reaction is preferably 25℃and the time is preferably 24 hours.
According to the invention, preferably, the alkyl alcohol is added into a two-neck round bottom flask, then the 1-carboxyethyl indoline spiropyran molecule and 4-dimethylpyridine are sequentially added, the obtained alkyl alcohol solution of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is slowly added dropwise into a reaction system, and stirring reaction is carried out for 24 hours in a normal temperature environment (25 ℃) to carry out dehydration condensation reaction, and in the process of the dehydration condensation reaction, the 1-carboxyethyl indoline spiropyran and hydroxyl groups on the alkyl alcohol are subjected to dehydration condensation reaction, so that the solid-state light-stimulated fluorescence rapid color-changing material is obtained.
In the present invention, the first dehydration condensation reaction preferably further comprises a post-treatment, and the post-treatment process is preferably that the obtained dehydration condensation reaction product is sequentially subjected to suction filtration, reduced pressure distillation and separation and purification by a silica gel column.
In the present invention, the suction filtration serves to remove insoluble matters in the dehydration condensation reaction.
The filtrate obtained by the suction filtration is preferably poured into a separating funnel, and the solvent in the filtrate is removed by the reduced pressure distillation.
In the invention, the eluent used for separating and purifying the silica gel column is petroleum ether-dichloromethane, and the volume ratio of petroleum ether to dichloromethane in the eluent is preferably 1:1.
when Ar is-C 5 H 10 NO, the preparation method comprisesThe method comprises the following steps:
and mixing an organic solvent, ethylamine, 1-carboxyethyl indoline spiropyran, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1-hydroxybenzotriazole to perform a second dehydration condensation reaction, so as to obtain the solid light-stimulated fluorescence rapid color change material.
In the invention, the molar ratio of the 1-carboxyethylindoline spiropyran, the ethylamine, the 1-hydroxybenzotriazole and the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:1.5:2:2.
in the present invention, the organic solvent is preferably anhydrous dichloromethane.
In the present invention, the temperature of the second dehydration condensation reaction is preferably 25℃and the time is preferably 24 hours.
In the invention, anhydrous methylene dichloride and ethylamine are preferably added into a two-port round bottom flask, and then 1-carboxyethyl indoline spiropyran molecules, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1-hydroxybenzotriazole are sequentially added. Stirring and reacting for 24 hours in a normal temperature environment (25 ℃) to carry out the second dehydration condensation reaction, wherein in the dehydration condensation reaction process, the amino groups on the 1-carboxyethyl indoline spiropyran and ethylamine are subjected to the dehydration condensation reaction to obtain the solid light-stimulated fluorescence rapid color-changing material.
In the present invention, the second dehydration condensation reaction preferably further comprises a post-treatment, and the post-treatment process is preferably that the obtained dehydration condensation reaction product is sequentially subjected to suction filtration, reduced pressure distillation and separation and purification by a silica gel column.
In the present invention, the suction filtration serves to remove insoluble matters in the dehydration condensation reaction.
The filtrate obtained by the suction filtration is preferably poured into a separating funnel, and the solvent in the filtrate is removed by the reduced pressure distillation.
In the invention, the eluent used for separating and purifying the silica gel column is petroleum ether-ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate in the eluent is preferably 1:2.
when Ar is-C 6 H 13 When the preparation method comprises the following stepsThe steps are as follows:
mixing an organic solvent, 2, 3-trimethyl-3H-indole and bromohexane, and performing a first reflux reaction to obtain a first reflux product;
and mixing the first reflux product, the organic solvent and the 5-nitro salicylaldehyde, and performing a second reflux reaction to obtain the solid-state light-stimulated fluorescence rapid color-changing material.
The invention mixes the organic solvent, 2, 3-trimethyl-3H-indole and bromohexane, and carries out a first reflux reaction to obtain a first reflux product.
In the present invention, the organic solvent is preferably anhydrous acetonitrile.
In one embodiment of the invention, anhydrous acetonitrile is preferably added into a two-neck round bottom flask, then 2, 3-trimethyl-3H-indole and bromohexane are sequentially added, the reaction device is placed in an oil bath pot for heating to perform the first reflux reaction for 24 hours, and the organic solvent is removed by reduced pressure distillation after the first reflux reaction is completed.
In the present invention, the time of the first reflux reaction is preferably 24 hours.
After a first reflux product is obtained, the first reflux product, an organic solvent and 5-nitrosalicylaldehyde are mixed, and a second reflux reaction is carried out, so that the solid light-stimulated fluorescence rapid color-changing material is obtained.
In the present invention, the organic solvent is preferably absolute ethanol.
In the present invention, the molar ratio of 2, 3-trimethyl-3H-indole, bromohexane and 5-nitrosalicylaldehyde is preferably 10:9.6:9.
in the present invention, the time of the second reflux reaction is preferably 20 hours.
After the second reflux reaction is finished, the obtained second reflux reaction product is distilled under reduced pressure to remove absolute ethyl alcohol, and the absolute ethyl alcohol is separated and purified by a silica gel column to obtain the solid light-stimulated fluorescence rapid color-changing material.
In the invention, the silica gel column is used for separating and purifying the mixed solution of petroleum ether and dichloromethane, wherein the volume ratio of petroleum ether to dichloromethane in the mixed solution is 3:1.
the invention also provides application of the solid-state light-stimulated fluorescence rapid color-changing material in the fields of reversible fluorescence color change and rapid color switching.
For further explanation of the present invention, the solid-state light-stimulated fluorescent rapid-color-changing materials provided by the present invention, as well as the preparation methods and applications thereof, are described in detail below with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
Preparation of solid-state light-stimulated fluorescence rapid color-changing material shown in 1
The synthesis steps are as follows: 5mL of a dry absolute ethanol solution was added to a 25mL two-necked round bottom flask, followed by sequential addition of 1-carboxyethylindoline spiropyran molecule (0.26 mmol,100 mg) and 4-lutidine (10 mg,0.08 mmol). To the reaction system was then slowly added dropwise a solution of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (95 mg,0.5 mmol) in absolute ethanol (4 mL). The reaction was stirred at ambient temperature for 24h.
Post-treatment: insoluble matters in the reaction were removed by suction filtration, the filtrate was collected and poured into a separating funnel, and the solvent in the filtrate was removed by distillation under reduced pressure. The final product was purified by column chromatography on silica gel (petroleum ether/dichloromethane, 1:1 v/v) to give the product as a white yellow powder (95.5 mg, 90%).
1 H NMR (500 mhz, acetate) δ=8.14 (d, j=2.7 hz, 1H), 8.05 (dd, j=9.0, 2.8hz, 1H), 7.17 (ddd, j=16.6, 16.1,9.1hz, 3H), 6.85 (dd, j=8.3, 5.7hz, 2H), 6.70 (d, j=7.7 hz, 1H), 6.05 (d, j=10.4 hz, 1H), 4.01 (q, j=7.1 hz, 2H), 3.66 (dt, j=14.8, 7.3hz, 1H), 3.56-3.50 (m, 1H), 2.74-2.66 (m, 1H), 2.62-2.55 (m, 1H), 1.27 (s, 3H), 1.16 (t, 6H) LC-MS (ESI: calculated values: m/z: 408.17: 409.48[ M+H ]] + . Elemental analysis (calculated) C67.6 (67.63), H5.9 (5.89), N6.8 (6.89), O19.6 (19.54).
Example 2
Preparation of solid-state light-stimulated fluorescence rapid color-changing material shown in 2
The synthesis steps are as follows: similar to the synthesis of formula 1, 9mL of the absolute ethanol solution was replaced with 9mL of the absolute propanol solution to prepare formula 2.
1 H NMR (500 mhz, acetate) δ=8.14 (d, j=2.6 hz, 1H), 8.05 (dd, j=9.0, 2.7hz, 1H), 7.23-7.12 (m, 3H), 6.85 (dd, j=8.0, 5.1hz, 2H), 6.71 (d, j=7.7 hz, 1H), 6.05 (d, j=10.4 hz, 1H), 3.92 (t, j=6.7 hz, 2H), 3.67 (dt, j=14.8, 7.4hz, 1H), 3.57-3.49 (m, 1H), 2.76-2.68 (m, 1H), 2.64-2.55 (m, 1H), 1.61-1.52 (m, 2H), 1.28 (s, 3H), 1.16 (s, 3H), 0.86 (t, j=7.7 hz, 2H): 3.57 (t, j=14.8, 7.4hz, 1H): the experimental value calculated as the MS 4 z: 422.87. elemental analysis (calculated) C68.23 (68.3), H6.2 (6.1), N6.6 (6.65), O18.9 (18.85).
Example 3
Preparation of solid-state light-stimulated fluorescence rapid-coloring material (c-SP) shown in 3
The synthesis steps are as follows: similar to the synthesis of formula 1, 9mL of the absolute ethanol solution was replaced with 9mL of the absolute butanol solution to prepare formula 3.
1 H NMR (500 mhz, acetate) δ=8.15 (d, j=2.6 hz, 1H), 8.05 (dd, j=9.0, 2.7hz, 1H), 7.17 (ddd, j=16.3, 15.7,8.8hz, 3H), 6.88-6.82 (m, 2H), 6.70 (d, j=7.8 hz, 1H), 6.05 (d, j=10.4 hz, 1H), 3.97 (t, j=6.7 hz, 2H), 3.66 (dt, j=14.8, 7.3hz, 1H), 3.57-3.50 (m, 1H), 2.75-2.68 (m, 1H), 2.60 (ddd, j=15.9, 7.6,6.2hz, 1H), 1.57-1.49 (m, 2H), 1.35-1.26 (m, 5H), 1.16.7 hz, 2H), 3.66 (dt, j=14.8, 7.3hz, 1H), 3.75-2.68 (m, 3H), 3.57-3H (k, 3H): 0.38 z (k, 3H): 436.95. elemental analysis (calculated) C68.8 (68.85), H6.5 (6.49), N6.4 (6.53), O18.3 (18.26).
Example 4
Preparation of solid-state light-stimulated fluorescence rapid color-changing material shown in 4
The synthesis steps are as follows: similar to the synthesis of formula 1, 9mL of the absolute ethanol solution was replaced with 9mL of the absolute pentanol solution to prepare formula 4.
1 H NMR (500 mhz, acetate) δ=8.14 (d, j=2.7 hz, 1H), 8.05 (dd, j=8.9, 2.7hz, 1H), 7.23-7.12 (m, 3H), 6.85 (dd, j=8.2, 5.7hz, 2H), 6.71 (d, j=7.8 hz, 1H), 6.05 (d, j=10.4 hz, 1H), 3.96 (t, j=5.9 hz, 2H), 3.66 (dt, j=14.8, 7.3hz, 1H), 3.58-3.49 (m, 1H), 2.72 (dt, j=14.5, 7.2hz, 1H), 2.64-2.55 (m, 1H), 1.59-1.52 (m, 2H), 1.31-1.24 (m, 7H), 1.16 (s, 3.86), 3.58 (t, j=14.8, 7.3hz, 1H), 3.58 (j=9 hz, 3H): 3.38 z/LC value (LC): ###] + . Elemental analysis (calculated) C69.3 (69.25), H6.7 (6.65), N6.2 (6.11), O17.8 (17.84).
Example 5
Preparation of solid-state light-stimulated fluorescence rapid color-changing material shown in 5
The synthesis steps are as follows: to a 25mL two-necked round bottom flask was added 5mL of dry anhydrous methylene chloride solution followed by 2mol/L of ethylamine (0.195 mL,0.39 mmol), 1-carboxyethylindoline spiropyran molecule (0.26 mmol,100 mg), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide (99.6 mg,0.52 mmol) and 1-hydroxybenzotriazole (0.52 mmol,70.2 mg) in this order. The reaction was stirred at ambient temperature (25 ℃) for 24h.
Post-treatment: insoluble matters in the reaction were removed by suction filtration, the filtrate was collected and poured into a separating funnel, and the solvent in the filtrate was removed by distillation under reduced pressure. The final product was purified by column chromatography on silica gel (petroleum ether/ethyl acetate, 1:2 v/v) to give the product as a pink powder (101 mg, 95%).
1 H NMR(500mhz, acetate) δ=8.13 (d, j=2.8 hz, 1H), 8.04 (dd, j=9.0, 2.8hz, 1H), 7.15 (ddd, j=16.5, 11.7,7.2hz, 3H), 7.07 (s, 1H), 6.83 (dd, j=11.3, 4.7hz, 2H), 6.70 (d, j=7.8 hz, 1H), 6.04 (d, j=10.4 hz, 1H), 3.65 (dt, j=14.7, 7.4hz, 1H), 3.50-3.41 (m, 1H), 3.16-3.08 (m, 2H), 2.51 (dt, j=14.4, 7.2hz, 1H), 2.43-2.35 (m, 1H), 1.26 (s, 3H), 1.15 (s, 3H), 1.00 (t=7.4 hz, 1H): 3.38 hz, 3H: 407.96. elemental analysis (calculated) C67.8 (67.72), H6.2 (6.28), N10.3 (10.15), O15.7 (15.85). .
Example 6
Preparation of solid-state light-stimulated fluorescence rapid color-changing material shown in 6
The synthesis steps are as follows: to a 50mL two-necked round bottom flask was added 10mL of dry anhydrous acetonitrile solution followed by 2, 3-trimethyl-3H-indole (10 mmol,1.6 g) and bromohexane (9.6 mmol,1.6 g) in sequence. The reaction apparatus was placed in an oil bath and heated under reflux for 24 hours, after the reaction, the organic solvent was distilled off under reduced pressure, 10mL of absolute ethyl alcohol, 5-nitrosalicylaldehyde (9 mmol,1.5 g) was added thereto, and the mixture was heated under reflux again for 20 hours. After the reaction, absolute ethanol was distilled off under reduced pressure, and the remaining mixture was purified by column chromatography on silica gel (petroleum ether/methylene chloride, 3:1 v/v) to give the product as pale yellow powder (3.6 g, 92%).
1 H NMR (500 mhz, acetate) δ=8.14 (d, j=2.7 hz, 1H), 8.05 (dd, j=9.0, 2.8hz, 1H), 7.20 (d, j=10.4 hz, 1H), 7.17-7.09 (m, 2H), 6.82 (dd, j=13.7, 8.1hz, 2H), 6.63 (d, j=7.7 hz, 1H), 6.06 (d, j=10.4 hz, 1H), 3.30-3.13 (m, 2H), 1.74-1.52 (m, 2H), 1.39-1.22 (m, 9H), 1.19 (s, 3H), 0.84 (t, j=6.9 hz, 3H) LC-MS (ESI): m/z: calculated value 392.21, experimental values: 393.12. elemental analysis (calculated) C73.4 (73.2), H7.2 (7.4), N7.1 (7.18), O12.2 (12.12).
Example 7
The solid state light stimulated fluorescent color-changing material powder prepared in example 1 was placed in a plastic petri dish, which was placed under a microscope. Photographs of the initial color of the powder in daylight and photographs of the non-fluorescent light in dark environment were taken, as shown in the left two photographs of fig. 1. Then, a 365nm ultraviolet lamp was placed over the petri dish, and the powder was continuously irradiated for 5 minutes, and then the ultraviolet lamp was turned off. At this point the white powder had changed to dark purple, in which the powder changed from the initial non-fluorescent state to the red fluorescent state, and again the purple and red fluorescent powder photographs were taken separately, as shown in the right two photographs of fig. 1. Then, the stimulus light source was switched to a green lamp of 524nm, and the color and fluorescence of the powder were restored to a state of not being irradiated by the ultraviolet lamp. According to the same operation, photochromic photographs of the solid powders of examples 2,3, 4, 5 and 6 under the light stimulus were taken sequentially, as shown in fig. 2 to 6. Photographs of the powder in fig. 1-6 showing fluorescence discoloration under visible light and in dark environments show that examples 1-6 all have better solid state light stimulated fluorescence discoloration properties.
Example 8
The powder of the photoinduced reversible color-changing material prepared in example 1 was placed on the surface of a barium sulfate substrate, pressed into a flat surface, and placed in a solid integrating sphere. The integrating sphere was placed in an ultraviolet-visible absorption spectrometer and tested to give an initial solid ultraviolet-visible absorption spectrum as shown in fig. 7 a). The initial powder had a distinct absorption peak at 337 nm. The integrating sphere was then turned on and the sample was exposed to a 365nm uv lamp for 5 minutes, the planar powder turning purple. The integrating sphere was turned off and the uv-vis absorption spectrum at this time was tested and the irradiated sample showed a new absorption peak at 560nm as shown in fig. 7 a. Subsequently, the integrating sphere was turned on again, and the purple sample was exposed to green light of 524nm or the like for irradiation for 30 minutes, and the planar powder color of the purple color was changed to the original color, and the absorption spectrum was restored to the original state. In a similar manner of operation, the powder of example 1 was tested for fluorescence spectrum variation, as shown in fig. 7 b), the starting powder did not have a distinct fluorescence emission peak under excitation by light, and after continued uv lamp irradiation, a distinct red fluorescence emission peak appeared at 664 nm. Likewise, the red fluorescence sample was illuminated with a 524nm green light, and the red fluorescence was gradually lost, eventually until the red fluorescence was turned off. Using the same procedure, examples 2-6 all exhibited similar properties of solid state light-stimulated red fluorescence switching.
Example 9
The material prepared in example 1 was placed in a solid integrating sphere according to the procedure of example 8, and was first tested for a material that was subjected to 365nm (3.5 mW/cm 2 ) The absorbance of the solid powder irradiated by the ultraviolet lamp varies as shown in fig. 8 a). The powder exhibits a new absorption peak at 564nm and its absorption value is gradually increasing, the absorption value of the material reaching substantially photostable after about 2 minutes of irradiation. Then, the illumination stimulus was switched to 524nm (12.21 mW/cm 2 ) The green light of (a) irradiates the powder as shown in fig. 8 b). The absorption of the powder at 564nm gradually decreases. The absorption value of the material was essentially 0 and the absorption peak completely disappeared at only 15 minutes of irradiation. The solid powder of example 1 was placed on a quartz plate and tested for 365nm (3.43 mW/cm 2 ) The intensity of fluorescence emission of the solid powder irradiated by the ultraviolet lamp varies as shown in fig. 8 c). The powder exhibits a new fluorescence emission peak at 688nm and its fluorescence intensity gradually increases, and after about 1 minute of irradiation, the fluorescence intensity of the material substantially reaches a light steady state. Then, similarly, the light stimulus was switched to 524nm (12.09 mW/cm 2 ) The green light of (d) irradiates the powder as shown in fig. 8. The fluorescence intensity of the powder at 688nm gradually decreased, and after only about 2 minutes of irradiation, the fluorescence intensity of the material was substantially 0, and the fluorescence peak was completely disappeared.
Example 10
The material (c-SP) prepared in example 3 was subjected to a slow solvent evaporation method to prepare an organic single crystal of the material, and the single crystal diffraction data was analyzed to obtain the crystal structure of the material. Meanwhile, the single crystal structure of the synthetic monomer 1-carboxyethylindoline spiropyran molecule (SP-COOH) having no photochromic property was examined, and as shown in FIGS. 9 a) and b), the single crystal structures of the SP-COOH and the material molecule prepared in example 3, respectively. It can be seen that the carboxyl group of SP-COOH results in strong hydrogen bonding between SP-COOH molecules, resulting in a closer distance between adjacent molecules. And the solid state light stimulated fluorescence rapid color change material prepared by the invention is reversely observed, and the hydrogen bond is destroyed due to the substitution of a long ester bond, so that the distance between two adjacent molecules is obviously increased. Next, the length parameters of the space planes formed by the four molecules in one unit cell are analyzed. As shown in FIGS. 9 c) and d), the length of the long oblique side and the diagonal line of the quadrangle formed between the SP-COOH molecules are obviously smaller than that of the quadrangle formed between the molecules of the material prepared in example 3, which indicates that the material prepared in example 3 has larger intermolecular distance in the space volume, and is favorable for the photoisomerization of the SP molecules. This further demonstrates that the series of molecules synthesized in this patent are able to successfully achieve solid state light to color changing properties, as compared to SP-COOH molecules that are unable to achieve photochromic properties.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (6)
1. A solid state light stimulated fluorescence rapid color change material has a structure shown in formulas 2-5:
2. the method for preparing the solid state light stimulated fluorescence rapid color change material according to claim 1, comprising the following steps:
the preparation method of the structure shown in the formulas 2-4 comprises the following steps:
mixing alkyl alcohol, 1-carboxyethyl indoline spiropyran, 4-lutidine and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide for a first dehydration condensation reaction to obtain the solid state light stimulated fluorescence rapid color change material; the alkyl alcohol is propanol, butanol or amyl alcohol;
the preparation method of the structure shown in the formula 5 comprises the following steps:
and mixing an organic solvent, ethylamine, 1-carboxyethyl indoline spiropyran, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1-hydroxybenzotriazole to perform a second dehydration condensation reaction, so as to obtain the solid light-stimulated fluorescence rapid color change material.
3. The preparation method according to claim 2, wherein the molar ratio of the 1-carboxyethylindoline spiropyran, ethylamine, 1-hydroxybenzotriazole to 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide is 1:1.5:2:2.
4. the method according to claim 2, wherein the first dehydration condensation reaction and the second dehydration condensation reaction are each carried out at a temperature of 25 ℃ for 24 hours.
5. The method according to claim 2, wherein the first dehydration condensation reaction and the second dehydration condensation reaction each further comprise a post-treatment, and the post-treatment comprises sequentially subjecting the obtained dehydration condensation reaction product to suction filtration, reduced pressure distillation and separation and purification by a silica gel column.
6. The use of the solid state light stimulated fluorescent rapid color change material of claim 1 in the fields of reversible fluorescent color change and rapid color switching.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210213790.6A CN114478559B (en) | 2022-03-07 | 2022-03-07 | Solid-state light-stimulated fluorescence rapid color-changing material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210213790.6A CN114478559B (en) | 2022-03-07 | 2022-03-07 | Solid-state light-stimulated fluorescence rapid color-changing material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114478559A CN114478559A (en) | 2022-05-13 |
| CN114478559B true CN114478559B (en) | 2023-05-12 |
Family
ID=81486328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210213790.6A Active CN114478559B (en) | 2022-03-07 | 2022-03-07 | Solid-state light-stimulated fluorescence rapid color-changing material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114478559B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403702A (en) * | 1991-03-13 | 1995-04-04 | Otsuka Kagaku Kabushiki Kaisha | Crystals consisting of an indolinospirobenzopyran derivative |
| CN105670389A (en) * | 2016-03-31 | 2016-06-15 | 吉林大学 | Reversible solid photochromic fluorescence ink material and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7410750B2 (en) * | 2004-06-30 | 2008-08-12 | Xerox Corporation | Multicolored photochromic display |
| CN102036994A (en) * | 2008-05-21 | 2011-04-27 | 巴斯夫欧洲公司 | Time temperature indicator comprising indolenin based spiropyrans containing N-acetylamido or N-acetylester side chain |
| US8298453B2 (en) * | 2010-01-06 | 2012-10-30 | Korea University Research And Business Foundation | Photochromic material |
| CN108148576A (en) * | 2018-03-05 | 2018-06-12 | 天津孚信阳光科技有限公司 | A kind of coloured bleach photochromic compound and preparation method thereof |
| CN110950879B (en) * | 2019-12-17 | 2023-07-04 | 浙江理工大学 | Spiropyran with introduced rigid radical to raise solid state photochromic performance and its synthesis process |
-
2022
- 2022-03-07 CN CN202210213790.6A patent/CN114478559B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5403702A (en) * | 1991-03-13 | 1995-04-04 | Otsuka Kagaku Kabushiki Kaisha | Crystals consisting of an indolinospirobenzopyran derivative |
| CN105670389A (en) * | 2016-03-31 | 2016-06-15 | 吉林大学 | Reversible solid photochromic fluorescence ink material and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114478559A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Seki et al. | Luminescent mechanochromic 9-anthryl gold (I) isocyanide complex with an emission maximum at 900 nm after mechanical stimulation | |
| CN109651293B (en) | Benzothiadiazole benzyl cyanide derivative and preparation method and application thereof | |
| CN110627800B (en) | Light reversible stimulus response fluorescent material and application thereof | |
| Lagref et al. | Artificial photosynthesis based on dye-sensitized nanocrystalline TiO2 solar cells | |
| McDonagh et al. | Organometallic complexes for nonlinear optics: Part 20. Syntheses and molecular quadratic hyperpolarizabilities of alkynyl complexes derived from (E)-4, 4′-HC CC6H4N NC6H4NO2 | |
| Zhang et al. | Tuning the fluorescence based on the combination of TICT and AIE emission of a tetraphenylethylene with D–π–A structure | |
| Mandal et al. | Influence of (2, 3, 4, 5, 6-pentamethyl/phenyl) phenyl scaffold: Stereoelectronic control of the persistence of o-quinonoid reactive intermediates of photochromic chromenes | |
| CN110256329B (en) | Fluorescent liquid crystal monomer containing alpha-cyano-containing stilbene structure, polymer and preparation method thereof | |
| Yam et al. | Synthesis, structure, and ion-binding properties of luminescent gold (I) alkynylcalix [4] crown-5 complexes | |
| Li et al. | Novel enantioselective fluorescent sensors for malate anion based on acridine | |
| CN114478559B (en) | Solid-state light-stimulated fluorescence rapid color-changing material, and preparation method and application thereof | |
| Fages et al. | Synthesis, structural, spectroscopic, and alkali-metal cations complexation studies of a bis-anthracenediyl macrotricyclic ditopic receptor | |
| Beer et al. | New alkynyl-and vinyl-linked benzo-and aza-crown etherbipyridyl ruthenium (II) complexes which spectrochemically recognize Group IA and IIA metal cations | |
| CN111574578B (en) | Circular polarization luminescent material with intelligent response multicolor conversion and preparation method and application thereof | |
| Hong et al. | Chemistry of the Tetraselenomolybdate Anion: Syntheses, Spectroscopic Results, and Structural Characterizations of Polynuclear Mo− Cu− Se Compounds Containing Thiolate Ligands | |
| CN113717231B (en) | AIE active force-induced light five-membered six-membered heterocyclic platinum complex, and preparation method and application thereof | |
| CN110041226B (en) | Compound with AIE characteristics and preparation method and application thereof | |
| CN109749732B (en) | Preparation method and application of photochromic/tribochromic luminescent material | |
| CN110128455B (en) | Preparation method of bornyl phenylethynyl BODIPY pH fluorescent probe | |
| CN113896736A (en) | Aryl-substituted spirooxazine photochromic compound and preparation method and application thereof | |
| Nakajima et al. | Thermal and photo substitution reactivity and crystal structures of tridentate Schiff base–ruthenium (II) complexes containing phosphorus or sulfur donor atoms | |
| CN111253381B (en) | Photochromic ligand, Re (I) rectangular supramolecular complex, and preparation method and application thereof | |
| CN113880880B (en) | Trinuclear silver (I) alkynyl complex with piezochromic property and preparation method and application thereof | |
| CN114907416B (en) | Selenium-containing purple-refined coordination metal macrocyclic supermolecule, and synthesis method and application thereof | |
| CN112079840B (en) | Indole derivative-thiophene compound and preparation 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 |