CN113024571B - Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof - Google Patents

Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof Download PDF

Info

Publication number
CN113024571B
CN113024571B CN202110312543.7A CN202110312543A CN113024571B CN 113024571 B CN113024571 B CN 113024571B CN 202110312543 A CN202110312543 A CN 202110312543A CN 113024571 B CN113024571 B CN 113024571B
Authority
CN
China
Prior art keywords
liquid crystal
fluorescence
color
spiropyran derivative
triple
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
Application number
CN202110312543.7A
Other languages
Chinese (zh)
Other versions
CN113024571A (en
Inventor
杨槐
胡威
孙畅
任云霄
秦晟煜
黄隽怡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Peking University
Original Assignee
Peking University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Peking University filed Critical Peking University
Priority to CN202110312543.7A priority Critical patent/CN113024571B/en
Publication of CN113024571A publication Critical patent/CN113024571A/en
Application granted granted Critical
Publication of CN113024571B publication Critical patent/CN113024571B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3483—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a non-aromatic 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • 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
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/13—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the technical field of thermotropic switches

Abstract

The invention discloses a spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal, and a preparation method and application thereof, wherein the spiropyran derivative is prepared by esterification reaction of 1',3',3' -trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline ] -5', 8-diol and para-position alkyl/alkoxy or alkyl/alkoxy substituted benzoic acid with an acrylate/methacrylate group at the chain end; the spiropyran derivatives are useful as molecular switches in smart materials. The spiropyran derivative disclosed by the invention has responsiveness to light, heat, pH value and force, has triple switchable effects of color, fluorescence and liquid crystal, has obvious difference in response behaviors due to different chemical environments, and is suitable for being used as a molecular switch in an intelligent material.

Description

Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof
Technical Field
The invention belongs to the field of molecular switches, and relates to a spiropyran derivative, in particular to a spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and a preparation method and application thereof.
Background
When a responsive functional molecule is stimulated by external chemical, electrochemical, or photochemical stimuli, the internal structure of the molecule changes, which results in changes in physical properties such as optical, electrical, and magnetic properties. Under the action of external conditions, the molecular structure of the molecule can be changed, so that molecular scale devices such as molecular switches, molecular logics and the like can be constructed, and the molecule has potential application prospects in the fields of information storage, anti-counterfeiting and the like, so that the molecule is continuously concerned by researchers in the industry.
A molecular switch is a simple molecular device that reversibly interconverts between different states (on and off) when exposed to an external stimulus. Common organic molecular switches capable of being excited by light include azobenzene, diarylethene, spiropyran and other compounds and derivatives thereof, which have the characteristics of reversible transformation of molecular structure or configuration and the like. Such microscopic changes in molecular structure or configuration can result in changes in macroscopic physical and chemical properties of the material, such as color, fluorescence, polarity, liquid crystallinity, and the like. The molecular material is widely applied to the fields of photoelectric devices, chemical sensing, drug controlled release and the like.
Azobenzene and diarylethene derivatives modified by liquid crystal elements are commonly used as functional molecules in liquid crystal intelligent materials, and are cis-trans isomeric under the stimulation of light, and a rod-shaped structure is changed into a V-shaped structure, so that the liquid crystal property is lost. Therefore, they may be liquid crystalline in the normal state and may be non-liquid crystalline after being stimulated from the outside, that is, they may be changed from a liquid crystalline ordered state to a non-liquid crystalline disordered state.
However, a compound which is normally non-liquid crystalline and becomes liquid crystalline when being stimulated by an external force, that is, a liquid crystalline molecule, is recently reported. However, compounds having triple switchable effects of color, fluorescence and liquid crystal properties have not been reported.
Disclosure of Invention
The invention aims to provide a spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal, so as to provide a compound with triple intelligent regulation and control of color, fluorescence and liquid crystal;
another object of the present invention is to provide a method for preparing the spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal;
it is still another object of the present invention to provide an application of the spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal.
In order to achieve the purpose, the invention adopts the technical scheme that:
a spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal property has a chemical structural formula as follows:
Figure BDA0002990437200000021
wherein the content of the first and second substances,
R1is O or CH2；
R2Is H,
Figure BDA0002990437200000022
Or is
Figure BDA0002990437200000023
n is any integer of 1 to 18.
The invention also provides a preparation method of the spiropyran derivative with the triple switch effects of color, fluorescence and liquid crystal, which is characterized in that 1',3',3' -trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline ] -5', 8-diol and para-position alkyl/alkoxy or alkyl/alkoxy substituted benzoic acid with an acrylate/methacrylate group at the chain end are subjected to esterification reaction to obtain the spiropyran derivative with the triple switch effects of color, fluorescence and liquid crystal;
wherein, the para-position has alkyl/alkoxy or the chemical structural formula of the alkyl/alkoxy substituted benzoic acid with the chain end being acrylate/methacrylate is as follows:
Figure BDA0002990437200000031
wherein the content of the first and second substances,
R1is O or CH2；
R2Is H,
Figure BDA0002990437200000032
Or is
Figure BDA0002990437200000033
n is any integer of 1-18;
the chemical reaction formula of the preparation method is as follows:
Figure BDA0002990437200000034
wherein R is1Is O or CH2；
R2Is H,
Figure BDA0002990437200000035
Or is
Figure BDA0002990437200000036
n is any integer of 1 to 18.
As a limitation, the esterification reaction is directly performed by dehydrating 1',3',3' -trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline ] -5', 8-diol and p-alkyl/alkoxy or alkyl/alkoxy substituted benzoic acid with an acrylate/methacrylate group at the chain end under the action of a dehydrating agent and a catalyst;
the chemical reaction formula of the esterification reaction is as follows:
Figure BDA0002990437200000041
wherein R is1Is O or CH2；
R2Is H,
Figure BDA0002990437200000042
Or is
Figure BDA0002990437200000043
n is any integer of 1 to 18.
As a further limitation, the dehydrating agent is dicyclohexylcarbodiimide and/or 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide;
the catalyst is at least one of triethylamine, N-diisopropylethylamine, N-dimethylaniline, pyridine and 4-dimethylaminopyridine;
the solvent of the esterification reaction is at least one of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, tetrahydrofuran and 1, 4-dioxane.
As a further limitation, the temperature of the esterification reaction is room temperature.
As another limitation, the esterification reaction is a phenol esterification reaction between benzoic acid substituted by alkyl/alkoxy at para-position or alkyl/alkoxy with an acrylate/methacrylate group at the chain end and an acyl chlorination reagent, and then under the action of an acid binding agent, the benzoic acid and 1',3',3' -trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline ] -5', 8-diol are subjected to the phenol chlorination reaction;
the chemical reaction formula of the esterification reaction is as follows:
Figure BDA0002990437200000044
wherein R is1Is O or CH2；
R2Is H,
Figure BDA0002990437200000051
Or is
Figure BDA0002990437200000052
n is any integer of 1 to 18.
By way of further limitation, the acid chlorination reagent is at least one of thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride;
the acid-applying agent is at least one of triethylamine, N-diisopropylethylamine, N-dimethylaniline, pyridine, 4-dimethylaminopyridine, triethanolamine, potassium carbonate, ammonium carbonate and sodium carbonate;
the solvent of the esterification reaction is at least one of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, tetrahydrofuran and 1, 4-dioxane.
As a further limitation, the temperature of the acyl chlorination reaction is 25-80 ℃;
the temperature of the phenol esterification reaction is 0-25 ℃.
And as a third limitation, after the esterification reaction is finished, cooling to 0-4 ℃, filtering, washing the obtained organic phase with water, drying, removing the organic solvent, purifying by column chromatography, and recrystallizing.
The invention also provides an application of the spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal as a molecular switch in an intelligent material.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
the spiropyran derivative with the triple switching effects of color, fluorescence and liquid crystal has responsiveness to light, heat, pH value and force, has triple switching effects of color, fluorescence and liquid crystal, and has obvious difference in response behaviors due to different chemical environments. The spiropyran derivative with the triple switch effects of color, fluorescence and liquid crystal is in a colorless or light-colored state, a non-fluorescent state and a non-liquid crystal state under a normal state; after being heated or irradiated by short-wavelength light, the fluorescent material changes into a state of deep color, strong fluorescence and liquid crystallinity; the substance can be returned to its original state after bright visible light irradiation; the compound is composed of two sections of ester liquid crystal elements, and the two sections of ester liquid crystal elements are in a V-shaped structure in an initial state, are not beneficial to the regular arrangement of molecules and have no liquid crystal property. When the ring is opened by external stimulation such as light, heat and the like, the molecular conjugation degree is greatly enhanced, the ring has strong absorption in a visible light area to generate color, and meanwhile, the ring has a photoluminescence characteristic, and the whole molecule is of a rod-shaped structure after the ring is opened, so that the liquid crystal phase is formed by regular arrangement of the molecules, and the liquid crystal property is realized.
The preparation method is used for preparing the spiropyran derivative with the triple switching effects of color, fluorescence and liquid crystal, the prepared spiropyran derivative with the triple switching effects of color, fluorescence and liquid crystal is suitable for being used as a molecular switch in an intelligent material, and the prepared intelligent material is applied to the fields of sensors, drivers, data storage, soft robots, high-resolution imaging systems and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a spiropyran derivative M1 produced in example 1 of the present invention;
FIG. 2 is a nuclear magnetic carbon spectrum of the spiropyran derivative M1 prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic hydrogen spectrum of a spiropyran derivative M1 having a 30% isomerization ring-opening product prepared in example 1 of the present invention;
FIG. 4 is a photograph taken under visible light, of an initial state of a spiropyran derivative M1 produced in example 1 of the present invention;
FIG. 5 shows the spiropyran derivative M1 prepared in example 1 of the present invention at a concentration of 5mW/cm-2After the 365nm ultraviolet light irradiates for 5 minutes, carrying out isomeric ring opening, and then taking a photo under the ultraviolet light;
FIG. 6 shows the spiropyran derivative M1 prepared in example 1 of the present invention at a concentration of 5mW/cm-2After the 365nm ultraviolet light irradiates for 5 minutes, isomerically opening the ring, and closing the photo shot by the ultraviolet light under the visible light;
FIG. 7 shows the initial state and the passage of 5mW/cm of a spiropyran derivative M1 prepared in example 1 according to the present invention-2365nm ultraviolet light irradiates for different time after isomerous ring opening (left) and after irradiating for 5 minutes, the ultraviolet absorption spectra after standing for different time (right) in the dark;
FIG. 8 shows the initial state and the passage of 5mW/cm of a spiropyran derivative M1 prepared in example 1 according to the present invention-2365nm ultraviolet light irradiates for 5 minutes to form a fluorescence spectrum after isomerization ring opening;
FIG. 9 is a DSC graph of the spiropyran derivative M1 produced in example 1 of the present invention;
FIG. 10 is a polarization image of liquid crystal texture at 85 ℃ of the spiropyran derivative M1 prepared in example 1 of the present invention;
FIG. 11 is a polarization texture image of a liquid crystal mixture N1 containing 5 wt% of a spiropyran derivative M1 in example 1, wherein the left image is a polarization texture image of an initial state of the liquid crystal mixture N1, and the middle image is a polarization texture image of the liquid crystal mixture N1 at a speed of 5mW/cm-2365nm ultraviolet radiation for 5sThe right image is the liquid crystal mixture N1 at 5mW/cm-2And a polarized texture image when the 365nm ultraviolet light is irradiated for 10 s.
Detailed Description
The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1 preparation method and application of a spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal
The structure of the spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal according to the embodiment is as follows:
Figure BDA0002990437200000071
the preparation process comprises the following steps:
dissolving 4.5kg of dicyclohexylcarbodiimide (DCC for short, 20mol) in 20L of dichloromethane (DCM for short) at room temperature in a dark condition to obtain a dehydrating agent solution;
3.5kg of 1',3',3 '-trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline are taken at room temperature under the condition of keeping out of the sun]Dissolving (20mol) 5', 8-diol (compound 1, 10mol) 5.9Kg of 4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid and (DMAP, 1mol) 122g of 4-dimethylaminopyridine in 30L of DCM, slowly dropwise adding a dehydrating agent solution (the dropwise adding time is about 2 hours and is generally controlled to be 0.5-5 hours), stirring at room temperature for esterification reaction for 24 hours after dropwise adding, detecting by TLC until the compound 1 is completely converted, stopping the reaction, cooling to 0 ℃, filtering to remove Dicyclohexylurea (DCU), washing the organic phase with 100L of water for 3 times, and then using MgSO (MgSO) as the organic phase4Drying, rotary evaporating to remove solvent to obtain crude product.
Under the conditions of room temperature and light protection, after the crude product is purified by column chromatography with eluent petroleum ether/dichloromethane (2: 1) and packed column silica gel (200-300 meshes), methanol is used for recrystallization twice, and the obtained yellowish solid is 6.0kg (total yield is 67%), namely the spiropyran derivative, which is marked as spiropyran derivative M1, the nuclear magnetic hydrogen spectrum of the spiropyran derivative is shown in figure 1, the nuclear magnetic carbon spectrum is shown in figure 2, and the nuclear magnetic hydrogen spectrum with partial isomerization ring-opening is shown in figure 3. The following characterization means such as absorption spectrum, fluorescence spectrum, liquid crystal texture polarization photograph prove that the spiropyran derivative M1 has triple switching effects of color, fluorescence and liquid crystal, and is a spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal.
The above reaction and post-treatment operations are carried out in the absence of light as much as possible.
The chemical reaction formula of the preparation process is as follows:
Figure BDA0002990437200000081
placing the spiropyran derivative M1 under visible light irradiation, see FIG. 4, that is, the initial state of spiropyran derivative M1, and moving it to 5mW/cm-2And after the 365nm ultraviolet light is irradiated for 5min, carrying out isomeric open loop, referring to fig. 5 (shooting under the ultraviolet light), and turning off the ultraviolet light and placing the ultraviolet light under visible light, referring to fig. 6 (turning off the ultraviolet light and shooting under the visible light). As can be seen from FIGS. 4 to 6, the spiropyran derivative M1 is light yellow in initial state, and emits red fluorescence under ultraviolet light after isomerization; turning off the UV light to a blue-violet color under visible light. It is shown that the spiropyran derivative M1 can change between light yellow and blue-violet, and can emit red fluorescence after isomerization.
The spiropyran derivative M1 was dissolved in tetrahydrofuran to prepare a 0.0625. mu. mol/L solution, which was measured in the initial state by an ultraviolet-visible spectrophotometer and passed through 5mW/cm-2365nm ultraviolet light irradiates for different time after the ring is opened (left) and after the ring is opened (right) after the ultraviolet light irradiates for 5 minutes and is placed in the dark for different time (right), referring to fig. 7, it can be seen that the ring opening isomerization of the spiropyran derivative M1 occurs along with the prolonging of the UV irradiation time, and the absorption peak appears around the wavelength of 580nm and is continuously enhanced; after 5 minutes of irradiation, the absorption peak reaches a maximum value, and after the sample is kept in the dark and is placed for different times, the absorption peak is continuously reduced to return to the initial state. Indicating that the spiropyran derivative M1 can act under UV lightThe ring-opened ring shows an absorption peak in the visible region under irradiation, so that a color change occurs, and the conversion is reversible.
The spiropyran derivative M1 was dissolved in tetrahydrofuran to prepare a 0.0625. mu. mol/L solution, and the initial state was measured with a fluorescence spectrophotometer and passed through 5mW/cm-2And 365nm ultraviolet light irradiates for 5min, and then the fluorescence spectrum after isomerization and ring opening is generated, referring to fig. 8, the spiropyran derivative M1 has no fluorescence in the initial state, and the fluorescence peak appears around 630nm after ring opening isomerization.
Taking the spiropyran derivative M1 to carry out measurement by using differential scanning calorimetry, the obtained DSC curve is shown in figure 9. As can be seen from FIG. 9, the spiropyran derivative M1 exhibited liquid crystal phase transition peaks at 80 ℃ and 90 ℃.
The spiropyran derivative M1 is poured into a liquid crystal box, the temperature is raised to 85 ℃, a polarized light photo of the liquid crystal texture is shot by using an electron microscope, and referring to fig. 10, the spiropyran derivative M1 has a good liquid crystal texture at 85 ℃.
Mixing a spiropyran derivative M1 into liquid crystal 5-amyl biphenylnitrile (5-CB), wherein the clearing point of the liquid crystal 5-CB is 35.8 ℃, obtaining a liquid crystal mixture (marked as N1) with the spiropyran derivative M1 content of 5 wt%, and taking a polarized light photograph of a liquid crystal texture by using an electron microscope, wherein the clearing point is reduced to 34.0 ℃ after the spiropyran derivative M1 is mixed, and the polarized light texture image of the liquid crystal mixture N1 is almost completely black at 34.0 ℃, but the color is 5mW/cm at the temperature of 5.8 DEG, as shown in the left picture in figure 11-2Bright LC textures appeared more and more upon 365nm uv illumination, see middle and right panels in fig. 11. As can be seen from fig. 11, the spiropyran derivative M1 has no liquid crystallinity in its initial state, and has liquid crystallinity after ring-opening isomerization by ultraviolet light irradiation.
In this embodiment, the spiropyran derivative M1 prepared as described above is used as a molecular switch in an intelligent material, and the prepared intelligent material is applied to the fields of sensors, drivers, data storage, soft robots, high-resolution imaging systems, and the like.
Examples 2 to 7 preparation method and application of spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal
Examples 2 to 7 are a method for preparing a spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal, and its application, respectively, the steps of which are substantially the same as those of example 1, except that the preparation method and the process parameters in its application are different, as detailed in table 1:
TABLE 1 summary of the process parameters of examples 2-7
Figure BDA0002990437200000101
Figure BDA0002990437200000111
The contents of the other portions of examples 2 to 7 are the same as those of example 1.
The structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 2 is as follows:
Figure BDA0002990437200000121
the chemical reaction formula of the preparation process in example 2 is:
Figure BDA0002990437200000122
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 3 is as follows:
Figure BDA0002990437200000123
the chemical reaction formula of the preparation process in example 3 is:
Figure BDA0002990437200000131
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 4 is as follows:
Figure BDA0002990437200000132
the chemical reaction formula of the preparation process in example 4 is:
Figure BDA0002990437200000133
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 5 is as follows:
Figure BDA0002990437200000141
the chemical reaction formula of the preparation process in example 5 is:
Figure BDA0002990437200000142
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 6 is as follows:
Figure BDA0002990437200000143
the chemical reaction formula of the preparation process in example 6 is:
Figure BDA0002990437200000151
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 7 is as follows:
Figure BDA0002990437200000152
the chemical reaction formula of the preparation process in example 7 is:
Figure BDA0002990437200000153
in embodiments 2 to 7, the prepared spiropyran derivatives M2 to M7 are used as molecular switches in an intelligent material, and the prepared intelligent material is applied to the fields of sensors, drivers, data storage, software robots, high-resolution imaging systems, and the like.
Example 8 preparation of a spiropyran derivative having triple switching effects of color, fluorescence and liquid crystallinity
The spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal related to the embodiment is the same as the spiropyran derivative in the embodiment 1, and the specific structure is as follows:
Figure BDA0002990437200000161
the preparation process comprises the following steps:
adding 5.9kg of 4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid (compound 2 for short, 20mol) and 3.6kg of thionyl chloride (30mol) into 10L of dichloromethane at room temperature under the condition of keeping out of the sun, carrying out acyl chlorination reaction at 30 ℃ until the compound 2 is completely converted by TLC detection, and then carrying out spin drying to obtain 6.2kg of acyl chlorination product;
at room temperature and in the dark, the obtained acyl chloride product is taken and mixed with 3.5kg of 1',3',3 '-trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline]Adding-5', 8-diol (compound 1, 10mol for short) into 8L dichloromethane, stirring for dissolving, adding 122g 4-dimethylaminopyridine, stirring at room temperature (25 ℃) for phenol esterification for 16h, detecting by TLC until the compound 1 is completely converted, stopping the reaction, cooling to 0 ℃, filtering, washing the organic phase with 100mL water for 3 times, and then using MgSO (MgSO) as the organic phase4Drying and rotary evaporating to removeAnd (5) dissolving to obtain a crude product.
Under the conditions of room temperature and light shielding, after the crude product is purified by column chromatography with an eluent of petroleum ether/dichloromethane (2: 1) and a packed column of silica gel (200-300 meshes), 5.7kg of an earthy yellow solid (total yield of 70%) is obtained by recrystallizing with methanol twice, namely the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal, which is marked as spiropyran derivative M8, and the nuclear magnetic hydrogen spectrogram and nuclear magnetic carbon spectrogram of the spiropyran derivative are the same as those of the spiropyran derivative M1 prepared in example 1, and the spiropyran derivative is determined to be the same compound.
The above reaction and post-treatment operations are carried out in the absence of light as much as possible.
The chemical reaction formula of the preparation process is as follows:
Figure BDA0002990437200000171
the spiropyran derivative M8 prepared by the embodiment can be used as a molecular switch in an intelligent material, and the prepared intelligent material is applied to the fields of sensors, drivers, data storage, soft robots, high-resolution imaging systems and the like.
Examples 9 to 14 methods for preparing spiropyran derivatives having triple switching effects of color, fluorescence and liquid crystallinity, and uses thereof
Examples 9 to 14 are a method for preparing a spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal, and its application, respectively, the steps of which are substantially the same as those of example 8, except that the preparation method and the process parameters in its application are different, as detailed in table 2:
TABLE 2 summary of the process parameters of examples 9-14
Figure BDA0002990437200000172
Figure BDA0002990437200000181
Wherein, one of the spiropyran derivatives M9-M14 corresponds to one of the spiropyran derivatives M2-M7, and the compounds prepared by the two methods correspond to the same compound one by one.
The contents of the other portions of examples 9 to 14 are the same as those of example 8.
The structure of the spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal related to the embodiment 9 is as follows:
Figure BDA0002990437200000191
the chemical reaction formula of the preparation process in example 9 is:
Figure BDA0002990437200000192
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 10 is as follows:
Figure BDA0002990437200000201
the chemical reaction formula of the preparation process in example 10 is:
Figure BDA0002990437200000202
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 11 is as follows:
Figure BDA0002990437200000203
the chemical reaction formula of the preparation process in example 11 is:
Figure BDA0002990437200000211
the structure of the spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal related to the embodiment 12 is as follows:
Figure BDA0002990437200000212
the chemical reaction formula of the preparation process in example 12 is:
Figure BDA0002990437200000221
the structure of the spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal referred to in example 13 is:
Figure BDA0002990437200000222
the chemical reaction formula of the preparation process in example 13 is:
Figure BDA0002990437200000223
the structure of the spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal according to example 14 is:
Figure BDA0002990437200000231
the chemical reaction formula of the preparation process in example 14 is:
Figure BDA0002990437200000232
in examples 9 to 14, the prepared spiropyran derivatives M9 to M14 were used as molecular switches in smart materials, and the prepared smart materials were applied to the fields of sensors, drivers, data storage, software robots, high-resolution imaging systems, and the like.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the claims.

Claims (10)

1. A spiropyran derivative with triple switch effects of color, fluorescence and liquid crystal is characterized in that the chemical structural formula is as follows:
Figure FDA0002990437190000011
wherein the content of the first and second substances,
R1is O or CH2；R2Is H,
Figure FDA0002990437190000012
Or is
Figure FDA0002990437190000013
n is any integer of 1 to 18.
2. The method for preparing the spiropyran derivative with the triple switch effects of color, fluorescence and liquid crystal according to claim 1, is characterized in that 1',3',3' -trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline ] -5', 8-diol and p-alkyl/alkoxy or alkyl/alkoxy substituted benzoic acid with an acrylate/methacrylate group at the chain end are subjected to esterification reaction to obtain the spiropyran derivative with the triple switch effects of color, fluorescence and liquid crystal;
wherein, the para-position has alkyl/alkoxy or the chemical structural formula of the alkyl/alkoxy substituted benzoic acid with the chain end being acrylate/methacrylate is as follows:
Figure FDA0002990437190000014
wherein the content of the first and second substances,
R1is O or CH2；R2Is H,
Figure FDA0002990437190000015
Or is
Figure FDA0002990437190000016
n is any integer of 1-18;
the chemical reaction formula of the preparation method is as follows:
Figure FDA0002990437190000021
wherein the content of the first and second substances,
R1is O or CH2；R2Is H,
Figure FDA0002990437190000022
Or is
Figure FDA0002990437190000023
n is any integer of 1 to 18.
3. The method for preparing a spiropyran derivative having triple switch effects of color, fluorescence and liquid crystal according to claim 2, wherein said esterification reaction is carried out by directly dehydrating 1',3',3' -trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline ] -5', 8-diol and alkyl/alkoxy-substituted benzoic acid having alkyl/alkoxy at para-position or having acrylate/methacrylate group at chain end under the action of dehydrating agent and catalyst;
the chemical reaction formula of the esterification reaction is as follows:
Figure FDA0002990437190000024
wherein the content of the first and second substances,
R1is O or CH2；R2Is H,
Figure FDA0002990437190000025
Or is
Figure FDA0002990437190000026
n is any integer of 1 to 18.
4. The method for preparing a spiropyran derivative having a triple switching effect of color, fluorescence and liquid crystal according to claim 3, characterized in that,
the dehydrating agent is dicyclohexylcarbodiimide and/or 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide;
the catalyst is at least one of triethylamine, N-diisopropylethylamine, N-dimethylaniline, pyridine and 4-dimethylaminopyridine;
the solvent of the esterification reaction is at least one of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, tetrahydrofuran and 1, 4-dioxane.
5. The method for preparing a spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal according to claim 3 or 4, wherein the temperature of said esterification reaction is room temperature.
6. The method for preparing a spiropyran derivative having a color, fluorescence and liquid crystal triple switch effect according to claim 2, wherein the esterification reaction is a phenol esterification reaction between benzoic acid substituted by alkyl/alkoxy at para-position or alkyl/alkoxy substituted by acrylate/methacrylate group at chain end and an acyl chlorination reagent, and 1',3',3' -trimethyl-6-nitro spiro [ benzopyran-2, 2' -indoline ] -5', 8-diol under the action of an acid-binding agent;
the chemical reaction formula of the esterification reaction is as follows:
Figure FDA0002990437190000031
，
wherein R is1Is O or CH2；R2Is H,
Figure FDA0002990437190000032
Or is
Figure FDA0002990437190000033
n is any integer of 1 to 18.
7. The method for preparing a spiropyran derivative having a triple switching effect of color, fluorescence and liquid crystal according to claim 6, characterized in that,
the acyl chlorination reagent is at least one of thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride;
the acid-binding agent is at least one of triethylamine, N-diisopropylethylamine, N-dimethylaniline, pyridine, 4-dimethylaminopyridine, triethanolamine, potassium carbonate, ammonium carbonate and sodium carbonate;
the solvent of the esterification reaction is at least one of dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, toluene, xylene, tetrahydrofuran and 1, 4-dioxane.
8. The method for preparing a spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal according to claim 6 or 7, characterized in that,
the temperature of the acyl chlorination reaction is 25-80 ℃;
the temperature of the phenol esterification reaction is-10-40 ℃.
9. The preparation method of the spiropyran derivative having triple switch effects of color, fluorescence and liquid crystal according to any one of claims 2-4, 6 and 7, characterized in that after the esterification reaction is finished, the temperature is further reduced to 0-4 ℃, then the product is filtered, and the obtained organic phase is washed with water, dried, removed of the organic solvent, purified by column chromatography and recrystallized.
10. Use of the spiropyran derivative having triple switching effects of color, fluorescence and liquid crystal according to claim 1 as a molecular switch in smart materials.
CN202110312543.7A 2021-03-24 2021-03-24 Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof Active CN113024571B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110312543.7A CN113024571B (en) 2021-03-24 2021-03-24 Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110312543.7A CN113024571B (en) 2021-03-24 2021-03-24 Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113024571A CN113024571A (en) 2021-06-25
CN113024571B true CN113024571B (en) 2022-01-11

Family

ID=76473250

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110312543.7A Active CN113024571B (en) 2021-03-24 2021-03-24 Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113024571B (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6521753B1 (en) * 2000-05-31 2003-02-18 Johnson & Johnson Vision Care, Inc. Indolinospiropyran compounds and methods for their manufacture
CN108976242A (en) * 2018-08-02 2018-12-11 南京大学 Synthesis a kind of while that there is photochromic and ion detection function Indoline spiropyran derivative
CN109651407B (en) * 2019-02-12 2021-06-15 赤峰学院 1, 8-naphthalimide light-operated fluorescent molecular switch compound bonded with double-spiropyran unit and synthetic method and application thereof
CN111606915B (en) * 2020-07-17 2021-06-15 浙大宁波理工学院 Preparation method of spiropyran photochromic material

Also Published As

Publication number Publication date
CN113024571A (en) 2021-06-25

Similar Documents

Publication Publication Date Title
CN109651407B (en) 1, 8-naphthalimide light-operated fluorescent molecular switch compound bonded with double-spiropyran unit and synthetic method and application thereof
Lutfor et al. Synthesis and characterization of bent-shaped azobenzene monomers: guest–host effects in liquid crystals with azo dyes for optical image storage devices
CN107603269B (en) Fluorescent dye based on naphthalimide, preparation method and application thereof
Liu et al. A naphthopyran-rhodamine based fluorescent and colorimetric chemosensor for recognition of common trivalent metal ions and Cu2+ ions
Wu et al. Photochromism of neutral spiropyran in the crystalline state at room temperature
Lonshakov et al. New fluorescent switches based on photochromic 2, 3-diarylcyclopent-2-en-1-ones and 6-ethoxy-3-methyl-1H-phenalen-1-one
Jiao et al. Photoresponsive organogel and organized nanostructures of cholesterol imide derivatives with azobenzene substituent groups
Zhang et al. A new organic far-red mechanofluorochromic compound derived from cyano-substituted diarylethene
Li et al. A novel multiphotochromic system with orthogonal light excitations
Shindy et al. Heptamethine and nonamethine cyanine dyes: novel synthetic strategy, electronic transitions, solvatochromic and halochromic evaluation
CN110256329B (en) Fluorescent liquid crystal monomer containing alpha-cyano-containing stilbene structure, polymer and preparation method thereof
Qu et al. A novel bis-acylhydrazone supramolecular gel and its application in ultrasensitive detection of CN−
CN108772027A (en) The preparation and application of a kind of supramolecular organogel and its metal gel
CN113024571B (en) Spiropyran derivative with triple switching effects of color, fluorescence and liquid crystal, and preparation method and application thereof
Yan et al. A novel azathia-crown ether dye chromogenic chemosensor for the selective detection of mercury (II) ion
EP1586618A1 (en) Photo-responsive liquid crystal composition
CN108822074B (en) Dithiophene ethylene compound with tetraphenylethylene unit and preparation method and application thereof
Kim et al. Crystalline-state photochromism and thermochromism of new spiroxazine
Lin et al. Visible light/Cu2+ dual triggered photochromic donor-acceptor stenhouse adducts: Synthesis, properties and applications
Hirano et al. Unusual fluorescent properties of novel fluorophores, 6-aryl-3, 4-diphenyl-α-pyrone derivatives
CN112218855A (en) NIR-II-emitting luminophores
Cao et al. Synthesis, structure and photophysical properties of three new hemicyanine dyes
Zheng et al. Photosensitivity enhancement of spiropyran-containing functional molecules by introducing flexible spacers and their application in smart color-changing textiles
CN108623543B (en) Furan derivative-containing triaryl ethylene photochromic material and its synthesis method and use
Chernyshev et al. Biphotochromic and ionochromic benzoxazolyl-substituted spirobipyrans

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