CN112159334A - Azobenzene molecular material with photoinduced solid-liquid conversion characteristic and synthesis method and application thereof - Google Patents
Azobenzene molecular material with photoinduced solid-liquid conversion characteristic and synthesis method and application thereof Download PDFInfo
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- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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Abstract
The invention relates to an azobenzene molecular material with a photoinduced solid-liquid conversion characteristic, and a synthesis method and application thereof. The azobenzene molecular material can generate trans-cis isomerization under the light induction, and the solid-liquid state of the molecule is changed due to the light-induced isomerization, so that reversible solid-liquid conversion can be generated at room temperature. Wherein the trans-azobenzene molecule is solid at room temperature and the cis-azobenzene molecule is liquid at room temperature. That is, photoisomerization may cause a reversible transition in molecular geometry between trans and cis, with a reversible transition in macroscopic states between solid and liquid. Therefore, the azobenzene molecular material of the present invention can switch its solid-liquid state by light, which has excellent photo-induced solid-liquid transition characteristics, not only on the micrometer scale, but more importantly, complete liquefaction and reversible solidification of a large number of samples can be clearly observed by the naked eye.
Description
Technical Field
The invention relates to the technical field of photoresponse molecular materials, in particular to an azobenzene molecular material with photoinduced solid-liquid conversion characteristics, and a synthesis method and application thereof.
Background
The solid-liquid state is an inherent property of organic molecules. For most organic molecules, the solid-liquid state of the organic molecules can be controlled by changing the ambient temperature through heating or cooling. The heat treatment method has the problems of high cost, large energy consumption and low control precision, and is difficult to realize the control of the partial solid-liquid state of the molecule.
Therefore, it is important to make the organic molecules realize reversible solid-liquid transition at room temperature by responding to external factors.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an azobenzene molecular material, a synthesis method and an application thereof, wherein the azobenzene molecular material can generate reversible solid-liquid transition at room temperature, and has excellent photo-induced solid-liquid transition characteristics. This is not only manifested on the micrometer scale, but more importantly, complete liquefaction and reversible solidification of a large number of samples can be clearly observed by the naked eye, and has a very short response time (solid-liquid transition time).
In order to solve the technical problems, the invention provides an azobenzene molecular material which is characterized by having a structure shown in a formula I:
according to the invention, through chemical structure design, the azobenzene molecular material with excellent photoinduced solid-liquid conversion characteristics at room temperature is obtained. The azobenzene molecular material of the formula I has a trans-configuration and a cis-configuration, and is respectively shown as a formula I- (E) and a formula I- (Z):
the trans-configured molecule of formula I- (E) is solid at room temperature and the cis-configured molecule of formula I- (Z) is liquid at room temperature. Under light-induced conditions, the molecules of the present invention can undergo isomerization, such as trans-to-cis conversion under ultraviolet irradiation, thereby causing solid-to-liquid conversion; under visible light irradiation, a cis-to-trans conversion may occur, which in turn causes a liquid to solid conversion.
Researches show that the azobenzene molecule has excellent photoinduced solid-liquid conversion characteristics. This is not only manifested on the micrometer scale, but more importantly, complete liquefaction and reversible solidification of a large number of samples can be clearly observed by the naked eye.
The trans-cis transformation and the phase transformation are shown in FIG. 2.
In another aspect, the present invention provides a method for synthesizing an azobenzene molecular material of formula I, comprising the steps of:
A) carrying out diazo coupling reaction on the arylamine compound shown in the formula I-a and phenol to obtain a compound shown in the formula I-b;
B) carrying out nucleophilic substitution reaction on the compound shown in the formula I-b and bromohexane to obtain an azobenzene molecular material shown in the formula I;
in some embodiments, in step a), the molar ratio of the arylamine compound of formula I-a to phenol is from 1:1.0 to 1: 1.3.
In some embodiments, in step B), the molar ratio of the compound of formula I-B to bromohexane is from 1:1.5 to 1: 3.
In some embodiments, in step a), the reaction is carried out in an ice water bath at a temperature of less than 5 ℃ for 1 to 24 hours.
In some embodiments, in step B), the reflux is stirred under an oil bath at 50-70 ℃ for 24-48 hours.
In some embodiments, in step a), the arylamine is converted to an aryldiazonium salt by slowly dropwise addition of an aqueous solution of sodium nitrite to a hydrochloric acid solution of the arylamine compound of formula I-a in an ice-water bath at a temperature of less than 5 ℃; and then, slowly dropwise adding an aqueous solution containing phenol, sodium hydroxide and potassium carbonate into a newly prepared diazonium salt solution under the condition of stirring to obtain a mixture with the pH of 9-10, continuing stirring for reaction for 2 hours, stopping the reaction, and acidifying, filtering, washing and recrystallizing the mixture to obtain the compound shown in the formula I-b.
In some embodiments, in step B), anhydrous potassium carbonate and bromohexane are added to the acetone solution of the compound of formula I-B, the reaction is stopped after the resulting mixture is placed under stirring and refluxing in a 60 ℃ oil bath for 24 hours, and the mixture is filtered, dried and recrystallized to give the azobenzene molecular material of formula I.
In another aspect, the present invention provides a method for performing a photo-induced solid-liquid conversion on the azobenzene molecular material or the azobenzene molecular material synthesized by the above synthesis method, comprising the steps of:
a) the trans-configuration azobenzene molecule shown in the formula I- (E) is converted into a cis-configuration azobenzene molecule shown in the formula I- (Z) under the irradiation of ultraviolet light at room temperature, so that the phase state is converted into a liquid state from a solid state; or
b) The azobenzene molecule shown in the formula I- (Z) with the cis-configuration is converted into the azobenzene molecule shown in the formula I- (E) with the trans-configuration under the irradiation of visible light at room temperature, so that the phase state is converted into a solid state from a liquid state; or
c) Repeating the steps a) and b) to realize reversible circulation of solid-liquid conversion.
In some embodiments, the ultraviolet light wavelength is 365 nm. In some embodiments, a 365nm wavelength LED light source is used.
In some embodiments, the visible light wavelength is 530 nm. In some embodiments, an LED light source with a wavelength of 530nm is used.
Compared with the prior art, the invention provides an azobenzene molecular material with a structure shown in a formula I. The azobenzene molecule can be isomerized under the light induction, so that the solid-liquid state before and after isomerization is changed, reversible solid-liquid conversion can be generated at room temperature, and the azobenzene molecule has excellent photoinduced solid-liquid conversion characteristics. This is not only manifested on the micrometer scale, but more importantly, complete liquefaction and reversible solidification of a large number of samples can be clearly observed by the naked eye, and has a very short response time (solid-liquid transition time). Therefore, the azobenzene molecule provided by the invention can solve the problems of high cost, large energy consumption, low control precision, difficulty in realizing control of the partial solid-liquid state of the molecule and the like in the heat treatment method for controlling the solid-liquid state of the organic molecule.
Drawings
Figure 1 shows the nmr hydrogen spectrum of an azobenzene molecule.
FIG. 2 shows the structural formula of trans-and cis-azobenzene molecules, photoisomerization and the liquefaction of the trans-solid sample under UV light (365nm LED light source) (20 μm scale).
Fig. 3 shows a macro camera photograph (scale 1cm) of a mass of trans-solid samples of azobenzene molecules liquefied under uv light (365nm LED light source) and a macro camera photograph (scale 1cm) of a liquefied sample solidified under visible light (530nm LED light source).
FIG. 4 shows the UV-VIS absorption spectrum of a reversible photoisomerization of an azobenzene molecule in chloroform solution.
Detailed Description
In order to further illustrate the present invention, the following will describe the azobenzene molecular material with photo-induced solid-liquid conversion property, its synthesis method and application in detail with reference to the examples.
The 4-n-butylaniline used in the following examples was purchased from Rone, concentrated hydrochloric acid, acetone, sodium nitrite, phenol, sodium hydroxide, anhydrous potassium carbonate, toluene and methanol from Chinese medicine, petroleum ether and ethyl acetate from Colon chemical, and bromohexane from Adamax.
Example 1
Synthesis of azobenzene molecules
1) 4-n-butylaniline (11.94g, 80mmol) and concentrated hydrochloric acid (20mL, 240mmol) were added to a 200mL beaker and dissolved, followed by the addition of 50mL acetone and 20g ice, and the mixture was stirred in an ice-water bath maintaining the solution temperature below 5 ℃; sodium nitrite (5.52g, 80mmol) was dissolved in 30mL of water and 10g of ice to prepare an aqueous sodium nitrite solution, which was placed in an ice water bath with the solution temperature kept below 5 ℃. Slowly dropwise adding the sodium nitrite aqueous solution into the mixture solution containing the 4-n-butylaniline under the stirring condition to generate the diazonium salt, and in the process, carefully supplementing ice water into the system to maintain the temperature of the system to be lower than 5 ℃ and prevent the generated diazonium salt from decomposing.
2) Phenol (7.52g, 80mmol), sodium hydroxide (3.24g, 81mmol) and potassium carbonate (11.06g, 80mmol) were dissolved in 20g of ice water to give a homogeneous clear solution; slowly dropwise adding the solution into the freshly prepared diazonium salt solution obtained in the step 1) under the condition of stirring to finally obtain a mixture with the pH of 9-10, and stopping the reaction after continuously stirring for 2 hours.
3) Under the condition of stirring, adding 1N hydrochloric acid into the reaction mixture for neutralization, adjusting the pH of the mixture to 3-4, continuously precipitating a reddish-brown solid particle in the system, and performing suction filtration and water washing on the mixed solution to obtain a reddish-brown crude product. The crude product was dried and recrystallized from toluene/petroleum ether to give 4- (4-n-butylbenzene) azophenol.
4) The product of step 3), 4- (4-n-butylbenzene) azophenol (3.81g, 15mmol), was weighed out and dissolved in 100mL of acetone, followed by the addition of anhydrous potassium carbonate (14.51g, 105mmol) and bromohexane (6.3mL, 45mmol), and the resulting mixture was placed in a 60 ℃ oil bath and stirred at reflux for 24 h. After the reaction was completed, the mixture was cooled to room temperature, insoluble substances such as inorganic salts were removed by filtration, the residue was washed with ethyl acetate, and the resulting orange filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, thereby obtaining a crude product of orange-yellow color. Carrying out thermal recrystallization on the crude product through methanol, and filtering to obtain a final azobenzene molecule: 4-butyl-4' -hexyloxy-azobenzene. Fig. 1 shows a nuclear magnetic hydrogen spectrum of the prepared azobenzene molecule.
Example 2
Photoinduced solid-liquid conversion of azobenzene molecules at micrometer scale
At room temperature, a small solid sample of azobenzene molecules (example 1) was placed on a smooth, clean glass slide, which was placed on the microscope stage at 365nm (3.9 mW/cm)2) The ultraviolet light irradiates the surface of the solid sample to cause the solid sample to generate photoisomerization, and after irradiating for 5 minutes, complete solid-liquid conversion is realized, and the initial solid sample is completely converted into liquid. Figure 2 shows liquefaction of a trans-solid sample under uv light irradiation.
Example 3
Complete liquefaction and reversible curing of large samples of azobenzene molecules
At room temperature, 12.18mg of azobenzene molecule (example 1) solid sample was weighed onto a smooth clean glass slide using 365nm (24.7 mW/cm)2) Ultraviolet light irradiates the surface of a solid sample to cause the solid sample to generate photoisomerization, after the irradiation is carried out for 15 minutes, a large number of samples are observed by naked eyes to realize complete solid-liquid conversion, the initial solid sample is completely converted into liquid, and the color is changed from yellow to red. Subsequently, the mixture was passed through a tube at 530nm (14.9 mW/cm)2) The cis-trans isomerization is induced by the irradiation of visible light, so that azobenzene molecules are solidified, after the irradiation is carried out for 15 minutes, a large number of samples are observed by naked eyes to realize complete liquid-solid conversion, the liquefied samples are completely converted into solids, and the color is changed from red to yellow. Fig. 3 shows that a number of samples of azobenzene molecules undergo phase inversion under uv and visible light illumination.
Example 4
Reversible photoisomerization of azobenzene molecules in chloroform solution
At room temperature, a small amount of azobenzene molecules (example 1) was dissolved in chloroform and the resulting solution was concentrated at 365nm (3.4 mW/cm)2) Irradiating the solution by using ultraviolet light to enable the solution to be subjected to photoisomerization, wherein after the solution is irradiated for 15 seconds, the ultraviolet-visible absorption spectrum of the solution is not changed any more, and the solution reaches a photostability state; subsequently, the mixture was passed through a tube at 530nm (7.6 mW/cm)2) The cis-trans isomerization is induced by visible light, after the illumination for 190 seconds, the ultraviolet-visible absorption spectrum of the solution is basically recovered to the initial state before the illumination, and no change occurs, namely, the solution reaches the light steady state. FIG. 4 shows UV-visible absorption of azobenzene molecules by reversible photoisomerization in chloroform solutionA spectrogram.
As can be seen from the above examples, the azobenzene molecule provided by the present invention has excellent photo-induced solid-liquid transition characteristics, which are not only expressed on the micrometer scale, but also more importantly, complete liquefaction and reversible solidification of a large number of samples can be clearly observed by the naked eye.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. An azobenzene molecular material is characterized by having a structure shown in a formula I:
2. the azobenzene molecular material of claim 1, having a trans configuration as shown in formula I- (E):
3. the azobenzene molecular material of claim 1, having a cis configuration as shown in formula I- (Z):
4. a method for preparing the azobenzene molecular material of claim 1, the method comprising the steps of:
A) carrying out diazo coupling reaction on the arylamine compound shown in the formula I-a and phenol to obtain a compound shown in the formula I-b; and is
B) Nucleophilic substitution reaction is carried out on the compound shown in the formula I-b and bromohexane to obtain azobenzene molecules shown in the formula I
5. The method according to claim 4, wherein in step A),
the molar ratio of the arylamine compound of formula I-a to phenol is 1:1.0 to 1: 1.3; and is
Reacting in ice water bath at the temperature lower than 5 ℃ for 1-24 hours.
6. The process of claim 4, wherein in step B), the molar ratio of the compound of formula I-B to bromohexane is from 1:1.5 to 1: 3; and is
Stirring and refluxing for 24-48 hours under the condition of oil bath with 50-70 deg.C.
7. A process as claimed in claim 4, wherein in step A), an aqueous solution of sodium nitrite is slowly added dropwise to a hydrochloric acid solution of the arylamine compound of formula I-a in an ice-water bath at a temperature below 5 ℃ to convert the arylamine into an aryldiazonium salt; and then, slowly dropwise adding an aqueous solution containing phenol, sodium hydroxide and potassium carbonate into a newly prepared diazonium salt solution under the condition of stirring to obtain a mixture with the pH of 9-10, continuing stirring for reaction for 2 hours, stopping the reaction, and acidifying, filtering, washing and recrystallizing the mixture to obtain the compound shown in the formula I-b.
8. The process according to claim 4, wherein in step B) anhydrous potassium carbonate and bromohexane are added to the acetone solution of the compound of formula I-B, the reaction is stopped after the resulting mixture is placed under stirring and refluxing in an oil bath at 60 ℃ for 24 hours, and the mixture is filtered, dried and recrystallized to obtain the azobenzene molecular material of formula I.
9. A method of subjecting the azobenzene molecular material of any one of claims 1-3 or prepared by the method of any one of claims 4-8 to a photo-induced solid-liquid transition, the method comprising the steps of:
a) the trans-configuration azobenzene molecule shown in the formula I- (E) is converted into a cis-configuration azobenzene molecule shown in the formula I- (Z) under the irradiation of ultraviolet light at room temperature, so that the phase state is converted into a liquid state from a solid state; or
b) The azobenzene molecule shown in the formula I- (Z) with the cis-configuration is converted into the azobenzene molecule shown in the formula I- (E) with the trans-configuration under the irradiation of visible light at room temperature, so that the phase state is converted into a solid state from a liquid state; or
c) Repeating the steps a) and b) to realize reversible circulation of solid-liquid conversion,
10. the method of claim 9, wherein the ultraviolet light wavelength is 365 nm; and is
Wherein the visible wavelength is 530 nm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5724780B2 (en) * | 1974-02-13 | 1982-05-26 | ||
| JP2006259565A (en) * | 2005-03-18 | 2006-09-28 | Fuji Photo Film Co Ltd | Optical recording medium and hologram recording method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5724780B2 (en) * | 1974-02-13 | 1982-05-26 | ||
| JP2006259565A (en) * | 2005-03-18 | 2006-09-28 | Fuji Photo Film Co Ltd | Optical recording medium and hologram recording method |
Non-Patent Citations (2)
| Title |
|---|
| WATSON, S. J.等: "A study of in situ isothermal phase transitions in photochromic liquid crystals", 《PROCEEDINGS OF SPIE-THE INTERNATIONAL SOCIETY FOR OPTICAL ENGINEERING》 * |
| 王明皓 等: "偶氮苯高分子的光致可逆固液转变", 《化学通报》 * |
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Application publication date: 20210101 |