CN114442341A - Electric response material with adjustable circular polarization luminescence property, device and preparation method - Google Patents
Electric response material with adjustable circular polarization luminescence property, device and preparation method Download PDFInfo
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- CN114442341A CN114442341A CN202111453682.8A CN202111453682A CN114442341A CN 114442341 A CN114442341 A CN 114442341A CN 202111453682 A CN202111453682 A CN 202111453682A CN 114442341 A CN114442341 A CN 114442341A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/0136—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour for the control of polarisation, e.g. state of polarisation [SOP] control, polarisation scrambling, TE-TM mode conversion or separation
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/061—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on electro-optical organic material
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Abstract
The invention provides an electric response material with adjustable circular polarization luminescence property, a device and a preparation method, and relates to the technical field of intelligent dimming, wherein the electric response material with adjustable circular polarization luminescence property comprises electric acid, electrobase and circular optical switch molecules with acid-base response; the electrogenerated acid is aniline derivative, the electrobase is p-benzoquinone derivative, and in the structural formula of circularly polarized optical switch molecule, R is1、R2Is hydrogen or an alkyl substituent, R3、R4Is hydrogen, phenyl or alkyl substituent, and R3And R4Are heterogeneous substituents. The invention utilizes the characteristic that 'electro-acid' aniline derivatives and 'electro-base' benzoquinone derivatives can reversibly release protons or take protons in the electrochemical oxidation or reduction process, and the characteristics of the 'electro-acid' aniline derivatives and the 'electro-base' benzoquinone derivatives and p-acidAnd the circularly polarized optical switch molecules with response to alkali are combined, so that the electric response material with adjustable circularly polarized luminescence property under the action of an electric field can be obtained, the required raw materials are simple and easy to obtain, and the construction cost of the device is low.
Description
Technical Field
The invention relates to the technical field of intelligent dimming, in particular to an electric response material with adjustable circular polarization luminescence property, a device and a preparation method.
Background
Circular polarization luminescence refers to the phenomenon that a chiral luminescent material emits left-handed or right-handed circularly polarized light after being excited by light or electricity. The material with the circularly polarized light emitting property capable of being intelligently switched has huge application potential in the fields of three-dimensional display, intelligent optical communication and the like, and has attracted extensive attention of people.
To date, circularly polarized optical switching materials based on various stimulation means have been developed, mainly solvents, acids/bases, mechanical forces, electricity, and the like. Among them, materials and devices with electrical response have been the focus of research due to their unique advantages in the preparation of optoelectronic devices. However, due to the limitation of the kinds of materials and the difficulty of device construction, the number of the currently developed circularly polarized optical switching materials and devices with electrical response is extremely limited, and the optical switching performance is not ideal, for example: the adjustable circularly polarized light has few kinds of optical states and poor optical switching stability.
Disclosure of Invention
The invention solves the problems that the number of the electric response circular polarization optical switch materials and devices developed in the prior art is extremely limited, and the optical switching performance is not ideal.
In order to solve the above problems, the present invention provides an electric response material with adjustable circular polarization luminescence property, comprising
Electroacid, electrobase and acid-base responsive circularly polarized optical switch molecules;
the electro-acid is an aniline derivative,
the electrobase is a p-benzoquinone derivative,
the structural formula of the circularly polarized optical switch molecule is as follows:
wherein R is1、R2Is hydrogen or an alkyl substituent, R3、R4Is hydrogen, phenyl or an alkyl substituent, and R3And R4Are heterogeneous substituents.
Preferably, the method for preparing the circularly polarized optical switch molecule comprises the following steps:
and step S1, adding the amino keto acid derivative A and resorcinol into an acidic solvent B at the temperature of 50-200 ℃, fully reacting, and purifying to obtain a product C.
And step S2, adding the product C and hexamethylenetetramine into an acid solvent D, fully reacting at 50-200 ℃, and purifying to obtain a product E.
And step S3, adding the product E and chiral benzylamine F into an organic solvent G, fully reacting, and purifying to obtain the circularly polarized optical switch molecule.
Preferably, in step S1, the molar ratio of the aminoketo acid derivative a to the resorcinol is 1.0 to 1.2; the aminoketo acid derivative A comprises 4-diethylaminoketo acid or 4-diisopropylaminoketo acid; the acidic solvent B comprises trifluoroacetic acid or methanesulfonic acid.
In step S2, the molar ratio of the product C to the hexamethylenetetramine is 1.0-1.5; the acidic solvent D comprises trifluoroacetic acid or methanesulfonic acid.
In step S3, the molar ratio of the product D to the chiral benzylamine F is 1.0 to 1.5; the chiral benzylamine F comprises R- (+) -alpha-methylbenzylamine or (R) -1- (pyridine-4-yl) ethylamine; the organic solvent G comprises absolute ethyl alcohol or dimethyl sulfoxide.
Compared with the prior art, the invention utilizes the characteristic that the 'electroic acid' aniline derivatives and the 'electrokali' benzoquinone derivatives can reversibly release protons or capture protons in the electrochemical oxidation or reduction process, and is combined with circularly polarized optical switch molecules which respond to both acid and alkali, so that the electric response material with adjustable circular polarization luminescence property under the action of an electric field can be obtained, the required raw materials are simple and easy to obtain, and the construction cost of the device is low.
In order to solve the technical problem, the invention also provides an electric device with adjustable circular polarization luminescence property, which comprises two transparent conductive electrodes and the electric response material with adjustable circular polarization luminescence property.
Compared with the prior art, the electric device with adjustable circular polarization luminescence property can realize reversible regulation and control of three circular polarization luminescence states in a visible light wave band under the control of proper electrical parameters, and respectively has no circular polarization luminescence property, left-hand circular polarization luminescence property and right-hand circular polarization luminescence property, has good stability, and has important application value in the field of intelligent optical modulation.
In order to solve the technical problem, the invention also provides a preparation method of the electric response device with adjustable circular polarization luminescence property, which comprises the following steps;
step T1, preparing a solution of circularly polarized optical switching layer, a solution of ion conducting layer and a solution of ion storage layer,
and T2, blade-coating the circularly polarized optical switching layer solution on one transparent conductive electrode, blade-coating the ion storage layer solution and the ion conductive layer solution on the other transparent conductive electrode, and after the solvent is dried, extruding the two transparent conductive electrodes loaded with the functional material together to obtain the electric response device with adjustable circularly polarized optical properties.
Preferably, in step T1, the method for disposing the circularly polarized optical switching layer solution includes:
stirring and completely dissolving 0-99% of film-forming agent, 0-99% of electrolyte, 0.01-99.9% of high-boiling-point organic solvent, 0.01-99.9% of circularly polarized optical switch molecule, 0.01-99.9% of electrobase and 0.01-99.9% of electroacid in low-boiling-point organic solvent.
Preferably, the method for preparing the ion conducting layer solution comprises the following steps:
stirring the film forming agent with the mass fraction of 0.01-99.9%, the electrolyte with the mass fraction of 0.01-99.9% and the high-boiling-point organic solvent with the mass fraction of 0.01-99.9% in the low-boiling-point organic solvent until the film forming agent, the electrolyte and the high-boiling-point organic solvent are completely dissolved.
Preferably, the method for preparing the ion storage layer solution comprises the following steps:
stirring the film forming agent with the mass fraction of 0.01-99.9%, the electrolyte with the mass fraction of 0.01-99.9%, the high boiling point organic solvent with the mass fraction of 0.01-99.9%, the functional molecule with the reduced characteristic with the mass fraction of 0.01-99.9% and the functional molecule with the oxidized characteristic with the mass fraction of 0.01-99.9% in the low boiling point organic solvent until the functional molecules are completely dissolved.
Preferably, the functional molecule with reduced property comprises p-benzoquinone, nitrobenzene, benzophenone, anthraquinone or dichlorobenzoquinone.
Preferably, the functional molecule with oxidation property comprises phenol, hydroquinone, aniline, p-phenylenediamine or thiophene.
Compared with the prior art, the electric response device with adjustable circular polarized luminescence property and the electric response material with adjustable circular polarized luminescence property have the same advantages, and are not repeated herein.
Drawings
FIG. 1 is a nuclear magnetic spectrum of an electro-acid molecule Urea-N in an example of the present invention;
FIG. 2 is a flow chart of a method for preparing a circularly polarized optical switch molecule R-Rhodol-A responsive to both acid and base in an embodiment of the present invention;
FIG. 3 is a nuclear magnetic spectrum of a circularly polarized optical switch molecule R-Rhodol-A responsive to both acid and base in an embodiment of the present invention;
FIG. 4 is a graph showing the analysis of the acid response of the circularly polarized optical switch molecule R-Rhodol-A responding to acid and base according to the embodiment of the present invention;
FIG. 5 is a diagram showing the analysis of the alkali response of the circularly polarized optical switch molecule R-Rhodol-A responding to acid and alkali according to the embodiment of the present invention;
FIG. 6 is a flow chart of a method for manufacturing an electrically responsive device with adjustable circularly polarized optical properties according to an embodiment of the present invention;
FIG. 7 is a CPL spectrum diagram of an electric response device with adjustable circularly polarized optical properties in an embodiment of the invention, wherein the electric response device is reversibly switched between triple circularly polarized optical states;
fig. 8 is a fluorescence emission spectrum of an electric response device with adjustable circularly polarized optical properties in an embodiment of the invention, which is reversibly switched between triple circularly polarized optical states.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It is noted that in the description of the present specification, the description of the term "some preferred embodiments" means that a particular feature, structure, material or characteristic described in connection with the embodiment or example is included in at least one preferred embodiment or preferred example of the present invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
With reference to fig. 1-5, embodiments of the present invention provide an electric response material with adjustable circular polarization luminescence property, including
Electrogenerated acid, electrobase and acid-base responsive circularly polarized optical switch molecules;
the electro-induced acid is an aniline derivative,
the electrobase is a p-benzoquinone derivative,
the structural formula of the circularly polarized optical switch molecule is as follows:
wherein R is1、R2Is hydrogen or an alkyl substituent, R3、R4Is hydrogen, phenyl or alkyl substituent, and R3And R4Are heterogeneous substituents.
Wherein R is1And R2Is hydrogen or an alkyl substituent, and R1And R2May be the same substituent or different substituents, R3And R4For a hetero substituent is meant R3And R4Are not the same substituent, and must be different substituents.
The embodiment utilizes the characteristic that the 'electro-acid' aniline derivatives and the 'electro-base' benzoquinone derivatives can reversibly release protons or take protons in the electrochemical oxidation or reduction process, and is combined with circularly polarized optical switch molecules which respond to both acid and base, so that the electro-responsive material with adjustable circular polarization luminescence property under the action of an electric field can be obtained, the required raw materials are simple and easy to obtain, and the construction cost of the device is low.
In some preferred embodiments, the electrogenic acid is selected from Urea-N, hydroquinone or hydroquinone diamine.
In some specific embodiments, Urea-N is prepared by the following method:
stirring and dissolving p-toluene isocyanate to obtain a clear and transparent solution, dropwise adding the solution into a tetrahydrofuran solution of N, N-dimethyl-p-phenylenediamine under the ice bath condition, reacting for 8-12 hours, separating out a large amount of gray precipitates, and after the reaction is finished, performing suction filtration and recrystallization to obtain the electro-acid which is a light gray solid.
In some preferred embodiments, the molar ratio of p-toluene isocyanate to N, N-dimethyl-p-phenylenediamine is 1: 1-1: 1.2.
in some preferred embodiments, the electrobase molecule is selected from coenzyme Q0, p-benzoquinone, or tetramethoxybenzoquinone.
In some preferred embodiments, as shown in fig. 2, the method for preparing the circularly polarized optical switch molecule comprises the following steps:
and step S1, adding the amino keto acid derivative A and resorcinol into an acidic solvent B at the temperature of 50-200 ℃, fully reacting, and purifying to obtain a product C.
And step S2, adding the product C and hexamethylenetetramine into an acid solvent D, fully reacting at 50-200 ℃, and purifying to obtain a product E.
And step S3, adding the product E and chiral benzylamine F into an organic solvent G, fully reacting, and purifying to obtain the circularly polarized optical switch molecule.
In some embodiments, in step S1, the molar ratio of the aminoketo acid derivative a to the resorcinol is 1.0 to 1.2; the aminoketo acid derivative A comprises 4-diethylaminoketo acid or 4-diisopropylaminoketo acid; the acidic solvent B comprises trifluoroacetic acid or methanesulfonic acid. In step S2, the molar ratio of the product C to the hexamethylenetetramine is 1.0-1.5; the acidic solvent D comprises trifluoroacetic acid or methanesulfonic acid. In step S3, the molar ratio of the product D to the chiral benzylamine F is 1.0 to 1.5; the chiral benzylamine F comprises R- (+) -alpha-methylbenzylamine or (R) -1- (pyridine-4-yl) ethylamine; the organic solvent G comprises absolute ethyl alcohol or dimethyl sulfoxide.
In some specific embodiments, the method for preparing the circularly polarized optical switch molecule comprises the following steps:
step S1, dissolving 4-diethylamino keto acid and resorcinol in trifluoroacetic acid, reacting at 85-95 ℃ for 12-16 hours, cooling to room temperature, drying the trifluoroacetic acid through vacuum rotary evaporation, dissolving the obtained solid in dichloromethane, extracting with saturated sodium bicarbonate water solution, and separating and purifying the obtained crude product to obtain an orange-red solid product;
step S2, dissolving the orange-red solid product and hexamethylenetetramine in trifluoroacetic acid, reacting at 85-95 ℃ for 12-16 hours, adding deionized water, continuing to react for 1-3 hours, cooling to room temperature, drying the trifluoroacetic acid through vacuum rotary evaporation, dissolving the obtained solid in dichloromethane, extracting with saturated sodium bicarbonate water solution, and separating and purifying the obtained crude product to obtain an orange solid product;
step S3, dissolving the orange solid product in absolute ethanol, adding R- (+) - α -methylbenzylamine, heating and refluxing for 4 to 6 hours, performing vacuum rotary evaporation to dry absolute ethanol, and separating and purifying the obtained crude product to obtain the circularly polarized optical switch molecule.
In some preferred embodiments, in steps S1-S3, the separation and purification is performed by column chromatography, and the eluents are methanol and dichloromethane, and in step S1, the ratio of the eluents is methanol: dichloromethane ═ 1:10 to 1:20, step S2, eluent ratio methanol: dichloromethane ═ 1:70-1:100, in step S3, the eluent ratio is methanol: dichloromethane ═ 1:60 to 1: 100.
In some preferred embodiments, in step S1, the molar ratio of the 4-diethylaminoketoacid to the resorcinol is 1.0 to 1.2;
in step S2, the molar ratio of the orange-red solid product to the hexamethylenetetramine is 1.0-1.5;
in step S3, the molar ratio of the orange solid product to the R- (+) - α -methylbenzylamine is 1.0 to 1.5.
Another embodiment of the present invention further provides an electrical device with adjustable circular polarization luminescence property, which includes two transparent conductive electrodes and the electrically responsive material with adjustable circular polarization luminescence property.
The electric device with adjustable circular polarization luminescence property of the embodiment can realize reversible regulation and control of three circular polarization luminescence states in a visible light wave band under the control of proper electrical parameters, wherein the three circular polarization luminescence states are respectively non-circular polarization luminescence property, left-hand circular polarization luminescence property and right-hand circular polarization luminescence property, and the electric device has good stability and has important application value in the field of intelligent optical modulation.
With reference to fig. 6, another embodiment of the present invention further provides a method for manufacturing an electric response device with tunable circularly polarized light emitting property, including the following steps;
step T1, preparing a solution of circularly polarized optical switching layer, a solution of ion conducting layer and a solution of ion storage layer,
and T2, blade-coating the circularly polarized optical switching layer solution on one transparent conductive electrode, blade-coating the ion storage layer solution and the ion conductive layer solution on the other transparent conductive electrode, and after the solvent is dried, extruding the two transparent conductive electrodes loaded with the functional material together to obtain the electric response device with adjustable circularly polarized optical properties.
It should be noted that, the transparent conductive electrode in this embodiment includes ITO glass or FTO glass, and the material is easily available.
In some preferred embodiments, in step T1, the method for preparing the circularly polarized optical switching layer solution includes:
stirring and completely dissolving 0-99% of film-forming agent, 0-99% of electrolyte, 0.01-99.9% of high-boiling-point organic solvent, 0.01-99.9% of circularly polarized optical switch molecule, 0.01-99.9% of electrobase and 0.01-99.9% of electroacid in low-boiling-point organic solvent.
In some preferred embodiments, the method for preparing the ion-conducting layer solution comprises:
stirring the film forming agent with the mass fraction of 0.01-99.9%, the electrolyte with the mass fraction of 0.01-99.9% and the high-boiling-point organic solvent with the mass fraction of 0.01-99.9% in the low-boiling-point organic solvent until the film forming agent, the electrolyte and the high-boiling-point organic solvent are completely dissolved.
In some preferred embodiments, the method of preparing the ion storage layer solution comprises:
stirring the film forming agent with the mass fraction of 0.01-99.9%, the electrolyte with the mass fraction of 0.01-99.9%, the high boiling point organic solvent with the mass fraction of 0.01-99.9%, the functional molecule with the reduced characteristic with the mass fraction of 0.01-99.9% and the functional molecule with the oxidized characteristic with the mass fraction of 0.01-99.9% in the low boiling point organic solvent until the functional molecules are completely dissolved.
The film-forming agent in the above embodiments includes polymethyl methacrylate, polyethylene, polystyrene, polyethylene glycol, polyethylene oxide, or polyoxyethylene. The material is easy to obtain, and the film forming effect is good.
The electrolyte comprises inorganic salts such as lithium perchlorate, lithium chloride, sodium chloride or potassium iodide and the like, or organic salts such as tetrabutylammonium tetrafluoroborate or tetramethylammonium hexafluorophosphate and the like.
The high boiling point organic solvent comprises propylene carbonate, ethylene carbonate, dimethyl sulfoxide, butyrolactone, anisole, nitrobenzene or trimethyl phosphate. The dissolving effect is good.
The low boiling point organic solvent comprises dichloromethane, trichloromethane, ethyl acetate, methanol or ethanol. The dissolving effect is good.
The functional molecule with reduced property comprises p-benzoquinone, nitrobenzene, benzophenone, anthraquinone or dichlorobenzoquinone. The material is easy to obtain and is easy to reduce.
The functional molecule with the characteristic of being oxidized comprises phenol, hydroquinone, aniline, p-phenylenediamine or thiophene. The material is easy to obtain and be oxidized.
Compared with the prior art, the electric response device with adjustable circular polarized luminescence property and the electric response material with adjustable circular polarized luminescence property have the same advantages, and are not repeated herein.
Example 1
The embodiment provides an electric response material with adjustable circular polarization luminescence property, which comprises:
electrogenerated acid, electrogenerated base and acid-base response circular optical switch molecules.
In this example, the electroluminescence material was prepared as follows: 0.68g N, N-dimethyl-p-phenylenediamine is added into a 100mL single-neck round-bottom flask, 15mL tetrahydrofuran is added as a solvent, after the mixture is stirred and dissolved into a clear and transparent solution, 0.67g of p-toluene isocyanate is dissolved into 15mL tetrahydrofuran, the solution is dropwise added into the tetrahydrofuran solution of the N, N-dimethyl-p-phenylenediamine under the ice bath condition, the reaction is carried out for 10 hours, and a large amount of gray precipitate is separated out. After the reaction is finished, filtering out the solid by suction, and recrystallizing by using methanol to obtain a final product, namely light gray solid Urea-N, wherein the yield is about 87%, and the specific synthetic route is as follows:
the nuclear magnetic spectrum of the electric acid obtained in this example is shown in fig. 1.
In this example, the electrobase molecule was selected from coenzyme Q0, 2, 3-dimethoxy-5-methyl-1, 4-benzoquinone, and was purchased directly.
In this embodiment, the synthetic route of the circularly polarized optical switch molecule R-Rhodol-A is as follows:
the preparation method comprises the following steps:
in step S1, 1.25g of 4-diethylaminoketoacid and 0.44g of resorcinol were put into a 30mL pressure-resistant tube, and about 15mL of trifluoroacetic acid was added as a solvent, and the above materials were dissolved by stirring. The system was warmed to 90 ℃ and stirred at this temperature for 12 hours. After the reaction was completed and cooled to room temperature, trifluoroacetic acid was evaporated to dryness under vacuum, and the resulting solid was dissolved in 35mL of dichloromethane. Then, extraction was repeated three times with 35mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was collected. The crude product is separated and purified by column chromatography, and the eluent ratio is methanol: 1-dichloromethane: 10, the final product is orange-red solid Rhodol. The yield was about 60%.
In step S2, 2.52g of orange-red solid Rhodol and 1.00g of hexamethylenetetramine were added to a 100mL single-neck round-bottom flask, and about 30mL of trifluoroacetic acid was added as a solvent, and the above materials were dissolved by stirring. The temperature of the system is increased to 90 ℃, the reaction is stirred for 14 hours at the temperature, then 5mL of deionized water is added into the reaction system, and the reaction is continued for 2 hours while the temperature is kept. After the reaction was completed and cooled to room temperature, trifluoroacetic acid was evaporated to dryness under vacuum, and the resulting solid was dissolved in 80mL of dichloromethane. Then, extraction was repeated three times with 80mL of a saturated aqueous sodium bicarbonate solution, and the organic phase was collected. The crude product is separated and purified by column chromatography, and the eluent ratio is methanol: 1-dichloromethane: 70, the final product is Rhodol-CHO as an orange solid with a yield of about 40%.
In step S3, 0.30g of orange solid Rhodol-CHO was added to a 100mL single-neck round-bottom flask, and about 40mL of absolute ethanol was added as a solvent and dissolved with stirring. Then, 102. mu. L R- (+) -alpha-methylbenzylamine was added to the above solution, and the reaction mixture was heated under reflux for 5 hours. After the reaction is finished, the absolute ethyl alcohol is rotated and evaporated to dryness under vacuum. The obtained crude product is separated and purified by column chromatography, and the eluent ratio is methanol: 1-dichloromethane: 60, the circularly polarized optical switch molecule R-Rhodol-A was obtained as an orange-red solid with a yield of about 40%. The nuclear magnetic spectrum of the prepared circularly polarized optical switch molecule is shown in fig. 3, and the acid-base response property of R-Rhodol-A is shown in fig. 4 and fig. 5, wherein, the graph A in fig. 4 shows the change of the dichromatic property of the acetonitrile solution of R-Rhodol-A under different acid adding conditions; b shows the change of photoluminescence property of R-Rhodol-A under different acid addition conditions, and C shows the change of absorbance property of acetonitrile solution of R-Rhodol-A under different acid addition conditions; d shows the color and fluorescence change of R-Rhodol-A in acetonitrile under different acid conditions. FIG. 5, panel A, shows the change of the dichromatic nature of an acetonitrile solution of R-Rhodol-A under different alkalinization conditions; b shows the change of photoluminescence property of R-Rhodol-A under different alkalifying conditions, and C shows the change of absorbance property of acetonitrile solution of R-Rhodol-A under different alkalifying conditions; d is a real picture showing the color change and fluorescence change of the acetonitrile solution of R-Rhodol-A under different alkali adding conditions. Therefore, it can be seen that, after different equivalents of chemical acid and chemical base are added into acetonitrile solution of R-Rhodol-A, the chiral property (circular dichroism), color and fluorescence of R-Rhodol-A all have obvious changes, and the response properties of acid and base are different.
The embodiment utilizes the characteristic that the 'electro-acid' aniline derivatives and the 'electro-base' benzoquinone derivatives can reversibly release protons or take protons in the electrochemical oxidation or reduction process, and is combined with circularly polarized optical switch molecules which respond to both acid and base, so that the electro-responsive material with adjustable circular polarization luminescence property under the action of an electric field can be obtained, the required raw materials are simple and easy to obtain, and the construction cost of the device is low.
Example 2
The embodiment provides a preparation method of an electric response device with adjustable circular polarization luminescence property, which comprises the following steps;
step T1, preparing a solution of circularly polarized optical switching layer, a solution of ion conducting layer and a solution of ion storage layer,
and T2, blade-coating the circularly polarized optical switching layer solution on one transparent conductive electrode, blade-coating the ion storage layer solution and the ion conductive layer solution on the other transparent conductive electrode, and after the solvent is dried, extruding the two transparent conductive electrodes loaded with the functional material together to obtain the electric response device with adjustable circularly polarized optical properties.
In this embodiment, in step T1, the method for preparing the circularly polarized optical switching layer solution includes:
0.1g of polymethyl methacrylate, 0.042g of tetrabutylammonium hexafluorophosphate, 0.021mL of propylene carbonate with 2mg of R-Rhodol-A, 0.15mg of coenzyme Q0 and 0.225mg of Urea-N were stirred in 1mL of acetonitrile until completely dissolved.
In this embodiment, in step T1, the method for preparing the solution for the ion conductive layer includes:
a mixture of 3.6g of polymethyl methacrylate, 1.5g of tetrabutylammonium hexafluorophosphate and 0.75mL of propylene carbonate in 20mL of acetonitrile is stirred until complete dissolution.
In this embodiment, the method for preparing the ion storage layer solution includes:
0.72g of polymethyl methacrylate, 0.30g of tetrabutylammonium hexafluorophosphate, 0.15mL of propylene carbonate, 54mg of p-benzoquinone and 110mg of hydroquinone were stirred in 10mL of acetonitrile until completely dissolved.
Referring to fig. 7-8, the electrically responsive device with tunable circularly polarized luminescence property prepared in this example shows different circularly polarized luminescence properties under different voltage parameters, and shows no circularly polarized luminescence property under no applied voltage, a left-handed CPL signal with an emission peak position of 558nm at-1.5V, a CPL signal with a left-handed emission peak position of 572nm at +1.5V, and can be reversibly returned to the initial state under the application of a small reverse voltage (+ 0.5V/-0.5V).
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. An electrically responsive material with adjustable circular polarized luminescence properties, comprising:
electrogenerated acid, electrobase and acid-base responsive circularly polarized optical switch molecules;
the electro-induced acid is an aniline derivative,
the electrobase is a p-benzoquinone derivative,
the structural formula of the circularly polarized optical switch molecule is as follows:
wherein R is1、R2Is hydrogen or an alkyl substituent, R3、R4Is hydrogen, phenyl or alkyl substituent, and R3And R4Are heterogeneous substituents.
2. The electrically responsive material with adjustable circularly polarized luminescence property of claim 1, wherein the preparation method of the circularly polarized optical switch molecule comprises the following steps:
step S1, adding the amino keto acid derivative A and resorcinol into an acidic solvent B at 50-200 ℃, fully reacting and purifying to obtain a product C;
step S2, adding the product C and hexamethylenetetramine into an acid solvent D, fully reacting at 50-200 ℃, and purifying to obtain a product E;
and step S3, adding the product E and chiral benzylamine F into an organic solvent G, fully reacting, and purifying to obtain the circularly polarized optical switch molecule.
3. The electrically responsive material with tunable circularly polarized light emitting property according to claim 2,
in step S1, the molar ratio of the aminoketo acid derivative a to the resorcinol is 1.0 to 1.2; the aminoketo acid derivative A comprises 4-diethylaminoketo acid or 4-diisopropylaminoketo acid; the acidic solvent B comprises trifluoroacetic acid or methanesulfonic acid;
in step S2, the molar ratio of the product C to the hexamethylenetetramine is 1.0-1.5; the acidic solvent D comprises trifluoroacetic acid or methanesulfonic acid;
in step S3, the molar ratio of the product D to the chiral benzylamine F is 1.0 to 1.5; the chiral benzylamine F comprises R- (+) -alpha-methylbenzylamine or (R) -1- (pyridine-4-yl) ethylamine; the organic solvent G comprises absolute ethyl alcohol or dimethyl sulfoxide.
4. An electrical device with adjustable circularly polarized light emission properties, comprising two transparent conductive electrodes and an electrically responsive material with adjustable circularly polarized light emission properties as claimed in any one of claims 1 to 3.
5. A method for preparing an electric response device with adjustable circular polarization luminescence property, which is used for preparing the electric response device with adjustable circular polarization luminescence property of claim 4, and is characterized by comprising the following steps;
step T1, preparing a solution of circularly polarized optical switching layer, a solution of ion conducting layer and a solution of ion storage layer,
and T2, blade-coating the circularly polarized optical switching layer solution on one transparent conductive electrode, blade-coating the ion storage layer solution and the ion conductive layer solution on the other transparent conductive electrode, and after the solvent is dried, extruding the two transparent conductive electrodes loaded with the functional material together to obtain the circularly polarized optical property-adjustable electric response device.
6. The method for preparing an electrically responsive device with tunable circularly polarized light emission property according to claim 5, wherein in step T1, the method for preparing the solution of circularly polarized optical switching layer comprises:
stirring and completely dissolving 0-99% of film-forming agent, 0-99% of electrolyte, 0.01-99.9% of high-boiling-point organic solvent, 0.01-99.9% of circularly polarized optical switch molecule, 0.01-99.9% of electrobase and 0.01-99.9% of electroacid in low-boiling-point organic solvent.
7. The method for preparing an electric response device with adjustable circular polarization luminescence property of claim 5, wherein the method for preparing the ion conducting layer solution comprises the following steps:
stirring and dissolving the film forming agent with the mass fraction of 0.01-99.9%, the electrolyte with the mass fraction of 0.01-99.9% and the high-boiling-point organic solvent with the mass fraction of 0.01-99.9% in the low-boiling-point organic solvent completely.
8. The method for preparing an electric response device with adjustable circular polarization luminescence property of claim 5, wherein the method for preparing the ion storage layer solution comprises the following steps:
stirring and completely dissolving 0.01-99.9% of film forming agent, 0.01-99.9% of electrolyte, 0.01-99.9% of high-boiling-point organic solvent, 0.01-99.9% of functional molecules with reduced property and 0.01-99.9% of functional molecules with oxidized property in low-boiling-point organic solvent.
9. The method for preparing an electric response device with adjustable circular polarization luminescence property of claim 8, wherein the functional molecule with reduced property comprises p-benzoquinone, nitrobenzene, benzophenone, anthraquinone or dichlorobenzoquinone.
10. The method for preparing an electric response device with adjustable circular polarization luminescence property of claim 8, wherein the functional molecule with oxidized property comprises phenol, hydroquinone, aniline, p-phenylenediamine or thiophene.
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