CN108373444A - Fluorescence viologen derivative and its application and preparation method - Google Patents
Fluorescence viologen derivative and its application and preparation method Download PDFInfo
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- 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
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The invention discloses a kind of fluorescence viologen derivative and its application and preparation methods, and a series of quick visualization solvent identifications, alkaline section pH value, temperature, NH are prepared for using solvent-thermal method3The novel viologen derivative of alkaline gas rapid sensitive discoloration detection.The line fluorescent viologen derivative synthetic method is simple simultaneously, and yield is high, and at low cost, fluorescence is strong；Purpurine electrochromic device discoloration and good cycling stability, coloring voltage is low, and discoloration is fast, easy to assembly.Fluorescence viologen derivative can show color and the fluorescence radiation variation of differentiation in different organic solvents, to reach detection and distinguish organic solvent effect.And novel purpurine is prepared into Test paper, detectability when solution state is remained, test paper can show different color changes to have the function that sensing detection identifies.The test of purpurine electrochromic device then shows that fluorescence viologen derivative has good potential using value in the fields such as electrochomeric glass and display.
Description
Technical field
The present invention relates to a kind of fluorescent material, off-color material and its application and preparation method, especially a kind of vinyl is purple
Smart substance or naphthalene acetyl purpurine substance and its application and preparation method are applied to chemical industry and field of material technology, special
It is not to be applied to colour development material, colorimetric sensor and electrochromic device technical field.
Background technology
Visual colorimetric sensor has with its simplicity and sensitivity in fields such as environmental Kuznets Curves, safety, industrial premises
The foreground of being widely applied.Purpurine, N, N bis- replace -4,4 '-bipyridine cation salt, are widely used earliest as herbicide.
Due to its special electron deficient, make it that reversible oxygen can occur under the environment conditionings such as different external light, heat, pressure, electricity
Change reduction reaction, while showing apparent color change, is a kind of very colorimetric material with application prospect.
Viologen derivative is widely used in the discoloration sensing material such as electroluminescent, photic, thermotropic, solvent, simultaneously because its is low
LUMO orbital energy levels and charge transfer characteristic, in supermolecule, biology, the fields such as OLED, ECD also achieve huge research
Progress.
Due to the problems such as stability of purpurine radical cation is poor, colour developing is not lasting, use condition is harsh.Therefore big
Most purpurine colourshifting process can only occur under non-aqueous solution and oxygen-free environment, this significantly limits it on more vast field
Application and development.Have the purpurine material of photoluminescent property rarely found simultaneously, mainly purpurine and the inorganic matter that have been reported that at present,
Compound and viologen polymer of the compositions such as supermolecule, ZIF, MOFs etc., and fluorescence quantum yield is not high, and simple hyperfluorescence
Purpurine material has not been reported.
Invention content
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Fluorescence viologen derivative and its application and preparation method synthesize acetophenone derivs or benzoic acid derivative as the new of substituent group
Type fluorescence viologen derivative, especially ethylene benzyl viologen substance or naphthalene acetyl purpurine substance, it is intended to develop it glimmering
The material and device of light anti-counterfeit recognition, solvent colour developing identification realize multi-functional detection sensing, colour developing and discoloration display etc., and real
Existing fluorescence viologen derivative of the present invention is in alkaline section pH, temperature, NH3The test paper of equal alkaline gas, electronic sensing devices and
The potential practical application in the fields such as electrochromic device and display device.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of fluorescence viologen derivative, molecular formula are as follows：
Wherein, A is 5~10 unit's heteroaryls optionally R 5~10 yuan of aryl replaced or optionally replaced by R；B is optional
5~10 unit's heteroaryls R 5~10 yuan of aryl replaced or optionally replaced by R；5~10 yuan of aryl refer to armaticity list
Ring or simultaneously ring substituents, ring atom number are any one atomicity in 5~10；The preferred phenyl of above-mentioned 5~10 yuan of aryl
And naphthalene；5~10 unit's heteroaryl refers to aromatic monocyclic, loop coil or simultaneously ring substituents, during ring atom number is 5~10
Any one atomicity, wherein at least have 1~3 be the hetero atom selected from N, O or S, wherein nitrogen-atoms be it is substituted or
It is unsubstituted, L be singly-bound andR is selected from H, F, Cl, Br, I, CN, NO2、OH、NH2、C1-6Alkyl, OC1-6Alkyl, NH
(C1-6Alkyl) or N (C1-6Alkyl) (C1-6Alkyl), the C1-6Alkyl, OC1-6Alkyl, NH (C1-6Alkyl), N (C1-6Alkyl)
(C1-6Alkyl) optionally replaced by F, Cl, Br or I；X is halogens.
As currently preferred technical solution, nitrogen or sulfur heteroatom are optionally aoxidized.
Above-mentioned 5~10 unit's heteroaryl preferably uses pyrrole radicals, pyrazolyl, imidazole radicals, oxazolyls, triazolyl, tetrazole radical, different
Oxazolyl, thiazolyl, furyl, thienyl, pyridyl group, pyrazinyl, pyrimidine radicals, benzothiazolyl, purine radicals, benzimidazole
Base, indyl, isoquinolyl, quinoxalinyl, quinolyl, pyrazinyl, purine radicals or phenyl Bing oxazolyls.
As currently preferred technical solution, fluorescence viologen derivative molecular formula is as follows：
X is F, Cl, Br or I.
The technical solution further preferred as the present invention, fluorescence viologen derivative molecular formula are as follows：
Wherein, R1、R2、R3、R4、R5、R6、R7And R8Separately it is selected from H, F, Cl, Br, I, CN, NO2、OH、NH2、C1-6
Alkyl, OC1-6Alkyl, NH (C1-6Alkyl) or N (C1-6Alkyl) (C1-6Alkyl), the C1-6Alkyl, OC1-6Alkyl, NH (C1-6Alkane
Base), N (C1-6Alkyl) (C1-6Alkyl) optionally replaced by F, Cl, Br or I, X F, Cl, Br or I.
As the technical solution of the present invention still more preferably, fluorescence viologen derivative molecular formula is as follows：
A kind of application of fluorescence viologen derivative of the present invention, using fluorescence viologen derivative as fluorescent functional material, and makees
It develops the color for solvent and distinguishes material, be applied in solvent colour developing recognition methods or gas colour developing recognition methods, or by fluorescence purpurine
Functional material of the derivative as sensor, or using fluorescence viologen derivative as the functional material of electrochromic device.
As currently preferred technical solution, fluorescence viologen derivative can be to liquid basified section pH, the fluid of fluid
Temperature or alkaline gas NH3The difference of concentration carries out the developing response for having differentiation, or carries out under different voltages having differentiation
Developing response realizes electrochromism function.
As currently preferred technical solution, fluorescence viologen derivative is carried on neutral paper material, inspection is made
Test paper；Or using fluorescence viologen derivative as electrochromism functional layer material, electrochromic device, electrochromism device is made
The electrochromism functional layer module of part includes electrolyte and its container, and the electrolyte includes electrolyte, to electrode substance and the moon
Pole substance, using fluorescence viologen derivative as the cathode substance.
The present invention provides a kind of quick visualization detection solvent, alkaline section pH value, temperature, NH3Equal alkaline gas
The preparation method of novel fluorescence viologen derivative, and provide the preparation of its application and Test paper in terms of fluorescence sense
The preparation method of technology and electrochromic device.The present invention is by reasonably designing so that the novel fluorescence purpurine pair synthesized
Alkaline solution has high ratio chromatic sensitivity, while the synthetic method of the fluorescence viologen derivative is simple, and fluorescence intensity is high；Purpurine
The preparation process of test paper is simple；Purpurine electrochromic device discoloration and good cycling stability, coloring voltage are low；With fine
Potential using value.
The synthetic reaction mechanism and preparation process of novel fluorescence viologen derivative of the present invention are as follows：
Wherein R is H, F, Cl, Br, I, CN, NO2、OH、NH2、C1-6Alkyl, OC1-6Alkyl, NH (C1-6Alkyl), N (C1-6Alkane
Base) (C1-6Alkyl) or other substituent groups, it is preferred with electron-withdrawing group, the C1-6Alkyl, OC1-6Alkyl, NH (C1-6Alkyl),
N(C1-6Alkyl) (C1-6Alkyl) optionally replaced by F, Cl, Br or I, X is halogen.
A kind of preparation method of fluorescence viologen derivative of the present invention, includes the following steps：
(1) bis- (4- pyridines) ethylene of 1,2- and halo acetophenone derivative are weighed as reactant, or weighs 1,2- is bis-
(4- pyridines) ethylene and benzoic acid derivative are as reactant；By bis- (4- pyridines) ethylene of 1,2- and halo acetophenone derivative
Quality proportioning is 1:2~1:4 ratio, or it is 1 to press bis- (4- pyridines) ethylene of 1,2- and the quality proportioning of benzoic acid derivative:
2~1:4 ratio, reactant is placed in reaction vessel, and anhydrous DMF, acetonitrile or acetone are then added into reaction vessel
Solvent makes reactant fully be dissolved, and obtains material system mixture solution, then by above-mentioned raw materials system mixture solution
1~48h of back flow reaction is carried out at 80~140 DEG C, light yellow or yellow sediment is made to generate, and is formed and is generated containing precipitation
The mixed liquor of object；Halo acetophenone derivative preferably use 2- chloro-acetophenones, 2- how bromide methyl ketone, the '-chlorine of 3,4- dihydroxy -2
Acetophenone or alpha-chloro -3,4- dichloroacetophenones；The benzoic acid derivative preferably uses 4- (2- acetyl bromides) benzoic acid；
(2) wait for being cooled to room temperature after reaction for the step (1), by containing precipitation product mixed liquor carry out from
Heart processing, isolated sediment anhydrous DMF and acetone are washed 3~6 times respectively, and the supernatant to after centrifuging is from brown
It becomes colorless, 4~12h is dried under vacuum and at a temperature of 60~80 DEG C in isolated solid substance, is obtained
To faint yellow, yellow, yellowish-brown, bronzing or pale powder, to obtain ethylene benzyl viologen, as fluorescence purpurine derives
Object.
The preparation method of another fluorescence viologen derivative of the present invention, includes the following steps：
A. 4,4'-Bipyridine and halo acetophenone derivative are weighed as reactant, by 4,4'-Bipyridine and halogeno-benzene second
The quality proportioning of ketone derivatives is 1:2~1:4 ratio, reactant is placed in reaction vessel, is then added into reaction vessel
Entering anhydrous DMF, acetonitrile or acetone solvent makes reactant fully be dissolved, and obtains material system mixture solution, then will
Above-mentioned raw materials system mixture solution carries out 1~48h of back flow reaction at 80~140 DEG C, and light-yellow precipitate object is made to generate, and is formed
Mixed liquor containing precipitation product；
B. it waits for being cooled to room temperature after reaction for the step a, the mixed liquor containing precipitation product is centrifuged
Processing, isolated sediment anhydrous DMF and acetone are washed 3~6 times respectively, until the supernatant after centrifugation becomes from brown
To be colourless, then at room temperature high purity water is added in isolated crude product into crude product dropwise, until crude product is all molten
It solves, forms crude product in solution, after acetone then is added into crude product in solution, there are a large amount of light-yellow precipitates to be precipitated, then will divide
4~12h is dried under vacuum and at a temperature of 60~80 DEG C from obtained solid substance, obtains pale yellow powder,
To obtain naphthalene acetyl purpurine, as fluorescence viologen derivative.
Due to the introducing of vinylpyridine, acetophenone derivs substituent group so that substituted acetophenone benzyl viologen of the invention
Derivative has the colour developing sensing sensitivity and Sequence of Relative Stability of Free Radicals for being substantially better than existing fluorescence viologen derivative, while also having
The excellent luminescent properties that other purpurines are lacked.Five kinds of fluorescence viologen derivatives of Vio1-5 that the present invention synthesizes are in the solution
All color developings with good solvent and alkali；Detailed research wherein is carried out by taking Vio1-2 fluorescence viologen derivatives as an example,
Research finds that both fluorescence viologen derivatives have excellent fluorescence property, and fluorescence quantum yield is high respectively in DMSO solution
Up to 31.48%, 54.40%, simultaneously because it is different in the photoluminescent property of different solvents, it is thus possible in fluorescence viologen derivative
The type of solvent is easily identified in the case of colour fading.Test strips are put into dry after being impregnated in fluorescence viologen derivative solution
There are one good sensing pH, temperature, NH for obtained purpurine test paper equally tool3, fluorescence performance.Importantly, of the invention
It is prepared for the electrochromic device of these novel fluorescence viologen derivatives, is groped by a series of experiment, the present invention can be prepared
Electrochromic device that can be practical.It can show apparent discoloration, and cyclical stability under the low-voltage of 0.1V
Well.
Fluorescence viologen derivative of the present invention is widely used, especially the application in following field：
One, fluorescence viologen derivative is identified and is applied to the fluorescence developing of organic solvent：
The a small amount of fluorescence viologen derivative for taking 0.1~1mg, is added separately in the different organic solvents of 10~20ml,
The preferred water of solvent, methanol, ethyl alcohol, DMF, DMA, MeCN, DMSO, PY, NMP, triethylamine, ethylenediamine or triethylene diamine.Pass through
Uv-visible absorption spectroscopy or naked eyes can easily distinguish the type of solvent according to the colour developing of different solvents.And work as
It, still can be simply by luminous colour developing phenomenon under ultra violet lamp and fluorescence spectrum after fluorescence viologen derivative solution decolourization
The type for identifying solvent, overcoming conventional purpurine cannot develop the color the defect of identification under bleached state.Fluorescence purpurine is spread out simultaneously
The test paper of biological solution processing also has apparent fluorescence radiation phenomenon, this shows the fluorescence viologen derivative in fluorescence sense and prevents
Pseudo- identification field has good potential application foreground.
Two, the preparation and application of fluorescence viologen derivative test paper：
The aqueous solution or alcoholic solution of a concentration of 1~20mmol/L of fluorescence viologen derivative are configured, it is spare.By neutral filter paper
Either neutral paper is cut into required strip or square, and the filter paper cut is then put into fluorescence viologen derivative
Dipping is no more than 30min in solution, takes out filter paper naturally dry, and sealed storage is spare as Test paper.
Three, detection and application of the fluorescence viologen derivative to alkaline solution pH：
The configuration of alkaline solution：Weigh a certain amount of sodium hydroxide be respectively configured pH be 7~14 alkaline aqueous solution it is spare.
The measurement of alkaline solution pH value：The aqueous solution of 1~3 drop pH value to be measured is added dropwise on purpurine test paper, examination is observed after 5s
Test paper color and standard color comparison card are carried out the pH value that comparison obtains solution to be measured by the color of paper, to prepare accurate alkalinity
PH test paper.
Four, application of the fluorescence viologen derivative to the detection sensing and temperature test paper of temperature：
The measurement of temperature：Purpurine test paper is placed on 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C
Series of temperature gradient environment in, after 5s observe test paper color, by test paper color carry out comparison distinguish different temperature
Degree, prepares temperature test paper.
The measurement of cyclical stability：At the same temperature by purpurine test paper, the process for colouring and fading is repeated.Through experiment
Test shows that the purpurine test paper has the cyclical stability of good thermochromism, can application.
Five, fluorescence viologen derivative is in NH3The application of the detection sensing of equal alkaline gas：
NH3Measurement：Purpurine test paper is placed under certain ammonium hydroxide atmosphere, colourless test paper becomes royal purple in 1s
Color, this purpurine test paper can rapid sensitive detection alkaline gas, 1s fades under acid atmosphere or 20s can take off after leaving ammonia atmosphere
Color has good cyclicity, can be potential for detecting alkaline gas leakage and Environmental safety supervision.
Six, fluorescence viologen derivative is applied to the Integration Assembly And Checkout step of electrochromic device：
(1) processing of electrically-conductive backing plate IT0：By electrically-conductive backing plate IT0 be placed in ethanol solution be cleaned by ultrasonic 10~
30min removes the dust and grease on surface, obtains clean IT0 substrates, is put into baking oven and is dried for standby；
(2) configuration of purpurine electrolyte：With TBAPF6For supporting electrolyte, Fc is to electrode substance, and fluorescence purpurine derives
Object is cathode electrochromic substance, is added in anhydrous DMSO solvents and the Vio for being configured to 1~10mmol/L is mixed evenly, 0.1~
1mol/L TBAPF6, the purpurine electrolyte of 1~10mmol/L Fc.
(3) device assembles：2 × 4cm that plastic sheet is cut into, intermediate hollow out are adhered to ito glass surface at concave,
It is assembled into box with another ito glass again, purpurine electrolyte is injected into device using capillarity, it is finally solid with waterproof light
Glue packaging.
(4) electrochromic device is tested：Purpurine electrochromic device is surveyed using Shanghai Chen Hua electrochemical workstation
Examination, under different voltage, tests discoloration and the cyclical stability of device.When test finds the electrochromic device obtained discoloration
Between it is short, reach 0.2s, transmitance difference is high, and performance is stablized, and the fields such as electrochomeric glass, display are applicable to.
Particularly, of the invention " 5~10 unit's heteroaryl " refers to aromatic monocyclic, loop coil or simultaneously ring substituents, former on ring
Subnumber is 5~10, wherein it is the hetero atom selected from N, O, S to have 1~3, wherein nitrogen-atoms is preferably substituted or unsubstituted,
That is N or NR, wherein R are H or other substituent groups, and are preferably quaternized, and nitrogen and sulfur heteroatom are preferably aoxidized, i.e. NO and S
(O)p, wherein p is 1 or 2, and the examples of 5~10 unit's heteroaryls includes but not limited to pyrrole radicals (including N- pyrrole radicals, 2- pyrrole radicals
With 3- pyrrole radicals etc.), pyrazolyl (including 2- pyrazolyls and 3- pyrazolyls etc.), imidazole radicals (including TMSIM N imidazole base, 2- imidazole radicals,
The), such as 4- imidazole radicals and 5- imidazole radicals oxazolyls (including 2- oxazolyls, 4- oxazolyls and 5- oxazolyls etc.), triazolyl (1H-1,
2,3- triazolyls, 2H-1,2,3- triazolyls, 1H-1,2,4- triazolyls and 4H-1,2,4- triazolyls etc.), tetrazole radical, isoxazoles
Base (3- isoxazolyls, 4- isoxazolyls and 5- isoxazolyls etc.), thiazolyl (including 2- thiazolyls, 4- thiazolyls and 5- thiazoles
Base etc.), furyl (including 2- furyls and 3- furyls etc.), thienyl (including 2- thienyls and 3- thienyls etc.), pyridine
Base (including 2- pyridyl groups, 3- pyridyl groups and 4- pyridyl groups etc.), pyrazinyl, pyrimidine radicals (including 2- pyrimidine radicals and 4- pyrimidine radicals
Deng), benzothiazolyl (including 5- benzothiazolyls etc.), purine radicals, benzimidazolyl (including 2- benzimidazolyls etc.), indoles
Base (including 5- indyls etc.), isoquinolyl (including 1- isoquinolyls and 5- isoquinolyls etc.), quinoxalinyl (including 2- quinolines
Quinoline base and 5- quinoxalinyls etc.), quinolyl (including 3- quinolyls and 6- quinolyls etc.), pyrazinyl, purine radicals, phenyl Bing oxazoles
Base.
Relational language definition of the present invention：
" singly-bound " indicates that two groups of its connection are connected directly, such asIn
L be singly-bound it is practical indicate be
" optional " or " optionally " refer to that the event then described or situation may but must not occur, and should
Description including the wherein described event or situation there is a situation where and the event or situation not there is a situation where.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the present invention synthesizes, the fluorescence viologen derivative synthetic method used is simple, product purity is high, yield is high and cost
It is low；
2. there is the novel fluorescence viologen derivative that the present invention synthesizes the colour developing of good solvent to distinguish energy under solution state
Power, while there is excellent fluorescence radiation performance, have in molecular recognition and the fields such as fluorescence developing label and anti-counterfeit recognition
Good potential using value；
3. novel fluorescence purpurine test paper prepared by the present invention is capable of the detection alkalinity section pH value, temperature, NH of rapid sensitive3
Equal alkaline gas, organic solvent, and the purpurine test paper has excellent fluorescence radiation performance have anti-counterfeit recognition function and ultraviolet
Stealth shows function under lamp, and test paper preparation process is easy, is suitable for practical promotion and application, has as multi-functional test paper good
Market application prospect；
4. fluorescence purpurine electrochromic device prepared by the present invention has good electrochromic property, Coloring Time is short,
Developing voltage is low, and performance is stablized, and cyclicity is good, can regulate and control electrochromism by adjusting the ingredient of voltage and purpurine electrolyte, and
Device is easily assembled without oxygen barrier, can be used for electrochomeric glass and field of display.
Description of the drawings
Fig. 1 is the nuclear magnetic resonance spectroscopy for the Vio1-6 fluorescence viologen derivatives that the embodiment of the present invention one is prepared to example six.
Fig. 2 is the Fourier infrared spectrum figure for the Vio1-6 fluorescence purpurines that the embodiment of the present invention one is prepared to example six.
Fig. 3 is that the embodiment of the present invention seven is derived using Vio1, Vio2 fluorescence purpurine prepared by embodiment one and embodiment two
Color of the object in different organic solvents.
Fig. 4 is that the embodiment of the present invention seven is derived using Vio1, Vio2 fluorescence purpurine prepared by embodiment one and embodiment two
Fluorescence picture in object organic solvent different at 365nm UV.
Fig. 5 is fluorescence spectra of the seven novel fluorescence purpurine of the embodiment of the present invention in different organic solvents.
Fig. 6 is that the embodiment of the present invention nine uses the colour developing of the fluorescence purpurine test paper of the preparation of embodiment eight at various ph values.
Fig. 7 is colour developing of the nine fluorescence purpurine test paper of the embodiment of the present invention in different organic solvents.
Fig. 8 is the colour developing of ten fluorescence purpurine test paper of the embodiment of the present invention at different temperatures.
Fig. 9 is 11 fluorescence purpurine test paper of the embodiment of the present invention in NH3Colour developing discolouration phenomena under atmosphere.
Figure 10 is that the colour developing sensing principle of the fluorescence purpurine test paper of the embodiment of the present invention seven~11 and electrochromic device shows
It is intended to.
Figure 11 is fluorescence purpurine electrochromic device the showing under various concentration and voltage that the present invention implements that 12 prepare
Color.
Figure 12 is the cyclical stability collection of illustrative plates of fluorescence purpurine electrochromic device prepared by the embodiment of the present invention 12.
Specific implementation mode
Said program is described further below in conjunction with specific examples of the implementation, the preferred embodiment of the present invention is described in detail such as
Under：
Embodiment one：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of preparation method of fluorescence viologen derivative, includes the following steps：
Weigh the 2- chloro-acetophenones of 1,2- bis- (4- pyridines) ethylene (bpe) and 5mmol (0.773g) of 2mmol (0.364g)
In single-necked flask, the anhydrous DMF that 6ml is added fully dissolves, then by said mixture solution at 120 DEG C back flow reaction
12h.There is light-yellow precipitate generation in reaction process, wait for being cooled to room temperature after reaction, mixture is centrifuged, precipitates with anhydrous
DMF and acetone wash 3~5 times respectively, until the supernatant after centrifugation becomes colorless from brown, the dry 8h of 80 DEG C of vacuum collects to obtain
0.689g pale yellow powders, to obtain ethylene benzyl viologen, the fluorescence purpurine calculated based on bis- (4- pyridines) ethylene of 1,2- is derived
Object Vio1 yields are 70.2%.
Experimental test is analyzed：
Experiment test, the physical property ginseng of the compound are carried out using fluorescence viologen derivative manufactured in the present embodiment as sample
Number：Referring to Fig. 1 to Fig. 2.Molecular formula：C28H24Cl2N2O2
Structural formula：
Molecular weight：491.41
Appearance：Pale yellow powder
1H NMR(DMSO,25℃)：δ 9.09 (d, J=6.7Hz, 2H), 8.54 (d, J=6.8Hz, 2H), 8.29 (s,
1H), 8.11 (d, J=7.3Hz, 2H), 7.83 (t, J=7.4Hz, 1H), 7.70 (t, J=7.7Hz, 2H), 6.53 (s, 2H)
ppm.Referring to Fig. 1 (a).
It is infrared：(KBr disc):3416,3015,2940,2839,1694,1634,1522,1433,1215,992,763,
686,554cm﹣ 1.Referring to Fig. 2 (a).
Embodiment two：
The present embodiment and embodiment one are essentially identical, are particular in that：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of preparation method of fluorescence viologen derivative, includes the following steps：
Weigh the 2- chloro-acetophenones of 1,2- bis- (4- pyridines) ethylene (bpe) and 5mmol (0.773g) of 2mmol (0.364g)
In single-necked flask, the anhydrous DMF that 6ml is added fully dissolves, then by said mixture solution at 120 DEG C back flow reaction
12h.There is light-yellow precipitate generation in reaction process, wait for being cooled to room temperature after reaction, mixture is centrifuged, precipitates with anhydrous
DMF and acetone wash 3~5 times respectively, until the supernatant after centrifugation becomes colorless from brown, the dry 8h of 80 DEG C of vacuum collects to obtain
0.689g pale yellow powders, to obtain ethylene benzyl viologen, the fluorescence purpurine calculated based on bis- (4- pyridines) ethylene of 1,2- is derived
Object Vio2 yields are 70.2%.
Experimental test is analyzed：
Experiment test, the physical property ginseng of the compound are carried out using fluorescence viologen derivative manufactured in the present embodiment as sample
Number：Referring to Fig. 1 to Fig. 2.Molecular formula：C36H28Br2N2O2
Structural formula：
Molecular weight：680.43
Appearance：Yellow powder
1H NMR(DMSO,25℃)：δ 9.12 (d, J=6.7Hz, 4H), 8.87 (d, J=9.4Hz, 2H), 8.57 (d, J=
6.8Hz, 4H), 8.28 (d, J=8.7Hz, 2H), 8.26 (d, J=7.9Hz, 2H), 8.19 (d, J=8.7Hz, 2H), 8.11 (d,
J=8.1Hz, 1H), 8.08 (dd, J=8.6,1.6Hz, 1H), 7.79 (dd, J=11.0,4.1Hz, 1H), 7.74 (t, J=
7.5Hz,1H),6.64(s,4H)ppm.Referring to Fig. 1 (b).
It is infrared：(KBr disc):3740,3423,3032,2967,1686,1630,1516,1470,1343,1179,
1121,994,858,755,553,471cm-1.Referring to Fig. 2 (b).
Embodiment three：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of preparation method of fluorescence viologen derivative, includes the following steps：
Weigh 3, the 4- bis- of 1,2- bis- (4- pyridines) ethylene (bpe) and 5mmol/L (0.933g) of 2mmol/L (0.364g)
In single-necked flask, the anhydrous DMF that 10ml is added fully dissolves hydroxyl -2 '-chloro-acetophenone, and then said mixture solution exists
Back flow reaction is for 24 hours at 120 DEG C.Have yellow mercury oxide generation in reaction process, wait for being cooled to room temperature after reaction, by mixture from
The heart, precipitation anhydrous DMF and acetone wash 3~5 times respectively, until the supernatant after centrifugation becomes colorless from brown, 80 DEG C of vacuum
Dry 8h collects to obtain 0.759g Red-brown powders, to obtain ethylene benzyl viologen, is calculated based on bis- (4- pyridines) ethylene of 1,2-
Fluorescence viologen derivative Vio3 yields be 68.4%.
Experimental test is analyzed：
Experiment test, the physical property ginseng of the compound are carried out using fluorescence viologen derivative manufactured in the present embodiment as sample
Number：Referring to Fig. 1 to Fig. 2.Molecular formula：C28H24Cl2N2O6
Structural formula：
Molecular weight：555.40
Appearance：Brown powder
1H NMR(DMSO,25℃)：δ 10.41 (s, 1H), 9.70 (s, 1H), 9.04 (d, J=6.8Hz, 2H), 8.50 (d,
J=6.9Hz, 2H), 8.24 (d, J=18.0Hz, 1H), 7.50 (dd, J=8.3,2.1Hz, 1H), 7.46 (dd, J=6.6,
2.1Hz, 1H), 7.00 (t, J=7.1Hz, 1H), 6.38 (s, 2H).Referring to Fig. 1 (c).
It is infrared：(KBr disc):3853,3740,3410,3050,2927,2747,1684,1635,1598,1521,
1463,1347,1290,1183,1126,814,758,672,625,541cm-1.Referring to Fig. 2 (c).
Example IV：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of preparation method of fluorescence viologen derivative, includes the following steps：
Weigh α-chlorine of 1,2- bis- (4- pyridines) ethylene (bpe) and 5mmol/L (1.117g) of 2mmol/L (0.364g)
Generation -3,4- dichloroacetophenones are in single-necked flask, and the anhydrous DMF that 10ml is added fully dissolves, then by said mixture solution
Back flow reaction is for 24 hours at 120 DEG C.There is yellow mercury oxide generation in reaction process, waits for being cooled to room temperature after reaction, by mixture
Centrifugation, precipitation anhydrous DMF and acetone wash 3~5 times respectively, until the supernatant after centrifugation becomes colorless from brown, vacuum 80
DEG C dry 8h collects to obtain 0.962g yellowish-brown powder, to obtain ethylene benzyl viologen, is based on bis- (4- pyridines) the ethylene meters of 1,2-
The fluorescence viologen derivative Vio4 yields of calculation are 76.3%.
Experimental test is analyzed：
Experiment test, the physical property ginseng of the compound are carried out using fluorescence viologen derivative manufactured in the present embodiment as sample
Number：Referring to Fig. 1 to Fig. 2.Molecular formula：C28H20Cl6N2O2
Structural formula：
Molecular weight：629.19
Appearance：Yellowish-brown powder
1H NMR(DMSO,25℃)：δ 9.00 (d, J=6.9Hz, 1H), 8.51 (d, J=6.7Hz, 1H), 8.34 (d, J=
1.9Hz, 1H), 8.21 (s, 1H), 8.05 (d, J=8.5Hz, 1H), 8.00 (d, J=8.2Hz, 1H), 6.45 (s, 1H).Referring to
Fig. 1 (d).
It is infrared：(KBr disc):3740,3418,3009,2931,2885,2829,1693,1635,1571,1521,
1473,1389,1342,1206,1028,973,821,711,549cm-1.Referring to Fig. 2 (d).
Embodiment five：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of preparation method of fluorescence viologen derivative, includes the following steps：
Weigh the 4- (2- of 1,2- bis- (4- pyridines) ethylene (bpe) and 5mmol/L (1.215g) of 2mmol/L (0.364g)
Acetyl bromide) in single-necked flask, the anhydrous DMF that 10ml is added fully dissolves benzoic acid, then said mixture solution is existed
Back flow reaction is for 24 hours at 120 DEG C.Have yellow mercury oxide generation in reaction process, wait for being cooled to room temperature after reaction, by mixture from
The heart, precipitation anhydrous DMF and acetone wash 3~5 times respectively, until the supernatant after centrifugation becomes colorless from brown, 80 DEG C of vacuum
Dry 8h collects to obtain 1.12g yellow powders, to obtain ethylene benzyl viologen, is calculated based on bis- (4- pyridines) ethylene of 1,2- glimmering
Light viologen derivative Vio5 yields are 83.8%.
Experimental test is analyzed：
Experiment test, the physical property ginseng of the compound are carried out using fluorescence viologen derivative manufactured in the present embodiment as sample
Number：Referring to Fig. 1 to Fig. 2.Molecular formula：C30H26Br2N2O6
Structural formula：
Molecular weight：668.33
Appearance：Pale powder
1H NMR(DMSO,25℃)：δ 9.05 (d, J=6.8Hz, 1H), 8.54 (d, J=6.9Hz, 1H), 8.25 (s,
1H), 8.21 (s, 2H), 8.20 (d, J=1.9Hz, 1H), 6.52 (s, 1H).Referring to Fig. 1 (e).
It is infrared：(KBr disc):3867,3740,3414,3038,2931,2601,2460,1948,1706,1635,
1568,1513,1473,1385,1338,1231,1112,998,863,812,764,677,544cm-1.Referring to Fig. 2 (e).
Embodiment six：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 1 and Fig. 2, a kind of preparation method of fluorescence viologen derivative, includes the following steps：
4,4 '-bipyridyls (1.56g, 10mmol) and 2- bromonaphthalenes ethyl ketone (6.23g, 25mmol) is weighed in 50mL single port to justify
In the flask of bottom, dissolved with anhydrous DMF (15mL).Solution back flow reaction 36h at 120 DEG C has the life of light-yellow precipitate object in the process
At.[3]Reaction terminates to be cooled to room temperature, and centrifuges to be washed respectively 3~5 times with anhydrous DMF and acetone after sediment, until washing lotion is from palm fibre
Yellow becomes almost colourless, obtains crude product.At room temperature, high purity water is added into crude product dropwise, until all dissolvings.Xiang Rong
After a large amount of acetone are added in liquid, there are a large amount of light-yellow precipitates to be precipitated.It is centrifuged out precipitation, after being dried in vacuo 8 hours, obtains product naphthalene second
Acyl group purpurine 4.81g is 68.1% based on the fluorescence viologen derivative Vio6 yields that 4,4'-Bipyridine calculates.
Experimental test is analyzed：
Experiment test, the physical property ginseng of the compound are carried out using fluorescence viologen derivative manufactured in the present embodiment as sample
Number：Referring to Fig. 1 to Fig. 2.Molecular formula：C38H30O2N2Br2
Structural formula：
Appearance：Yellow powder
1H NMR(DMSO,25℃)：δ 9.37 (d, J=8.5,4H, ArH), 8.96 (d, J=9.0,4H, ArH), 8.20
(d, J=10.5,4H, ArH), 8.03 (d, J=10.5,4H, ArH), 7.58-7.47 (m, 6H, ArH), 6.69 (s, 4H).Referring to
Fig. 1 (f).
It is infrared：(KBr disc):3000,2933,2637,2404,1964,1690,1632,1569,1506,1459,
1359,1326,1263,1175,1127,1022,941,909,857,812,755,554,482cm-1.Referring to Fig. 2 (f).
Embodiment seven：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 3, Fig. 4 and Fig. 5, fluorescence viologen derivative senses the fluorescence developing of organic solvent
Test and application, steps are as follows：
No. 2 fluorescence purpurines prepared by No. 1 fluorescence viologen derivative Vio1 and embodiment two prepared due to embodiment one are spread out
The photoluminescent property of biological Vio2 is preferable, thus the present embodiment carries out the fluorescence of organic solvent using 1, No. 2 fluorescence viologen derivatives
Experiment is distinguished in colour developing, is taken the novel fluorescence viologen derivative of 1mg to be added in different organic solvents, is observed these organic solutions
Color change.Wherein, Fig. 3 (a) is colour developing experimental results of the Vio1 of a concentration of 0.2mmol/L in different organic solvents
Photo；Fig. 3 (b) is colour developing experimental result photos of the Vio2 of a concentration of 0.2mmol/L in different organic solvents.From Fig. 3
Photo in can find out 1, No. 2 fluorescence viologen derivatives can effectively distinguish methanol, ethyl alcohol, DMF, DMA, DMSO, PY,
The organic solvents such as NMP, triethylamine, ethylenediamine, triethylene diamine, wherein Vio1 develop the color to triethylamine, ethylenediamine, triethylene diamine
The color is too dark, thus dilutes 400,1000,400 times respectively.
And after fluorescence viologen derivative solution decolourization, by the fluorescence radiation situation of the solution under ultraviolet lamp in Fig. 4 and
Fluorescence spectrum in the different solvents of Fig. 5 can also distinguish the type of organic solvent.And both fluorescence viologen derivatives
All show excellent fluorescence property.Its quantum yield and fluorescence lifetime are respectively Фvio1=31.48%, Фvio2=
54.40%；τvio1=3.80ns, τvio2=3.68ns.Wherein, Fig. 4 (a) be under the ultra violet lamp of 365n, it is a concentration of
Fluorescence of the Vio1 of 0.2mmol/L in different organic solvents and colour developing experimental result photo；Fig. 4 (b) is in the ultraviolet of 365n
Under light irradiation, the fluorescence and colour developing experimental result photo of the Vio2 of a concentration of 0.2mmol/L in different organic solvents；Fig. 5 (a)
It is fluorescence spectras of the Vio1 of a concentration of 0.2mmol/L in EtOH solvents；Fig. 5 (b) is the Vio1 of a concentration of 0.2mmol/L
Fluorescence spectra in DMSO solvents；Fig. 5 (c) is fluorescence spectrums of the Vio2 of a concentration of 0.2mmol/L in EtOH solvents
Figure；Fig. 5 (d) is fluorescence spectras of the Vio2 of a concentration of 0.2mmol/L in DMSO solvents.
No. 1 fluorescence viologen derivative is dissolved in water, methanol, DMSO equal solvents, is write on filter paper with the solution
" SHU " can clearly find out these test paper luminescence phenomenon with hyperfluorescence in the UV lamp by Fig. 5, and fluorescence is being surveyed
Obviously do not decay in the half a year of examination, it means that these fluorescence viologen derivatives are in anti-counterfeit recognition and fluorescent marker sensory field
Has good potential using value.
Embodiment eight：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, a kind of application of fluorescence viologen derivative, neutral papery is carried on by fluorescence viologen derivative
On material, Test paper is made.
In the present embodiment, using the preparation purpurine test paper method of fluorescence viologen derivative, include the following steps：
Configuration concentration is the aqueous solution or alcoholic solution of the fluorescence viologen derivative Vio1-6 of 1~20mmol/L, spare.It will
Either neutral paper is cut into required strip or square to neutral filter paper, and the filter paper cut is then put into fluorescence purple
0~30min is impregnated in smart derivative solution, takes out filter paper naturally dry, and sealed storage is spare as pH Test papers.
Embodiment nine：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Fig. 6 and Fig. 7, the inspection to pH value of solution and solvent is made using eight purpurine test paper of embodiment
Sensor is surveyed, is included the following steps：
The preparation of alkaline solution：Weigh a certain amount of sodium hydroxide be respectively configured pH be 7~14 alkaline aqueous solution it is spare.
The making of standard color comparison card：The alkaline aqueous solution of the different pH value of 1~3 drop is added dropwise on purpurine test paper, is observed after 10s
The color of test paper prepares standard color comparison card according to the difference of different pH value and test paper color.As can be seen from Figure 6 with pH
The raising of value, the color of purpurine test paper are become red, purple, are finally changed to blue by faint yellow.
The differentiation of alkali organic solvent：1~3 drop organic solvent to be measured is added dropwise on purpurine test paper, test paper is observed after 5s
Color change, such as Fig. 7 it can be seen that different organic solvents shows different colors on purpurine test paper, to distinguish
Different organic solvents.
Embodiment ten：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, detection sensing testing of the purpurine test paper to temperature：
Purpurine test paper prepared by embodiment three is placed on 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C,
In the environment of 120 DEG C of series of temperature gradients, the color of test paper is observed after 5s.Pass through Fig. 8, it can be seen that as temperature is from 50 DEG C
During being increased to 120 DEG C, the color of purpurine test paper becomes au bleu from initial white and then gradually deepens to become bluish violet,
Temperature test paper can be prepared according to experimental phenomena.
The measurement of cyclical stability：At the same temperature by purpurine test paper, the process for changing colour and fading is repeated.Through experiment
Test shows that the purpurine test paper has the cyclical stability of good thermochromism, and warm mutagens can be preserved in 1 month by having
The performance of color practical can be promoted.
Embodiment 11：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, detection sensing testing of the purpurine test paper to alkaline gas such as NH3：
NH3Measurement：Purpurine test paper prepared by embodiment three is placed on to a series of NH of concentration gradients3In environment, observation
The color of test paper finds that test paper becomes bluish violet, the color of the more big then purpurine test paper of concentration of ammonia under ammonia atmosphere from Fig. 9
It is deeper.And test paper can gradually fade to original state after leaving ammonia atmosphere to have the performance for meeting ammonia colour developing again,
The acceleration that middle HCl gases can the be exceedingly fast colour fading process.The present embodiment is tested the cyclical stability of purpurine test paper, surveys
Examination finds that the simple purpurine test paper can keep stable ammonia to detect sensing capabilities in 15 days, this shows that this purpurine test paper exists
The alkaline gas such as sensing detection ammonia are revealed and food product environment safety monitoring aspect has good potential application foreground.
Figure 10 is the colour developing sensing principle schematic diagram of the purpurine test paper of embodiment seven~11 and electrochromic device.The present invention
Above mentioned embodiment provide a kind of quick visualization detection solvent, alkaline section pH value, temperature, NH3The fluorescence of equal alkaline gas
The preparation method of viologen derivative, and provide the technology of preparing and electricity of its application and Test paper in terms of fluorescence sense
The preparation method of mutagens color device.The present invention is by reasonably designing so that the fluorescence viologen derivative synthesized is molten to alkalinity
Liquid has high ratio chromatic sensitivity, while the synthetic method of the fluorescence viologen derivative is simple, and fluorescence intensity is high；Purpurine test paper
Preparation process is simple；Purpurine electrochromic device discoloration and good cycling stability, coloring voltage are low；With potential well
Application value.
Embodiment 12：
The present embodiment is substantially the same as in the previous example, and is particular in that：
In the present embodiment, referring to Figure 11 and Figure 12, the application of fluorescence viologen derivative described in a kind of claim 1, will
Functional material of the fluorescence viologen derivative as electrochromic device.The present embodiment is using fluorescence viologen derivative as electrochromism
Electrochromic device is made in functional layer material, and the electrochromism functional layer module of electrochromic device includes electrolyte and its appearance
Device, the electrolyte includes electrolyte, to electrode substance and cathode substance, using fluorescence viologen derivative as the cathode object
Matter.
In the present embodiment, the remaining test of a kind of preparation of purpurine electrochromic device, steps are as follows：
(1) processing of electrically-conductive backing plate IT0：Electrically-conductive backing plate IT0 is placed in acetone, ethanol solution with ultrasonic cleaning
30min removes the dust and grease on surface, obtains clean IT0 substrates, is put into baking oven and is dried for standby；
(2) configuration of purpurine electrolyte：With TBAPF6For supporting electrolyte, Fc is to electrode substance, and No. 1 fluorescence purpurine is spread out
Biology is cathode substance, is added in anhydrous DMSO solvents to be mixed evenly and is configured to 2mmol/L Vio1,0.1mol/L
TBAPF6, the purpurine electrolyte of 2mmol/L Fc；
(3) device assembles：2 × 4cm that plastic sheet is cut into, intermediate hollow out are adhered to ito glass surface at concave,
It is assembled into box with another ito glass again, the electrolyte of fluorescence viologen derivative Vio1-6 is injected into device using capillarity
In part, waterproof light binding packaging is finally used；
(4) electrochromic device is tested：Using Shanghai Chen Hua electrochemical workstation CHI660 to the electroluminescent change of the purpurine of assembling
Color device is tested.
Figure 11 is the Vio1 fluorescence viologen derivative electrochromic devices using the preparation of embodiment one in various concentration and electricity
The colour developing of pressure.Figure 12 is that 300 times of the Vio1 fluorescence viologen derivative electrochromic devices prepared using embodiment one are reversible
Discoloration cycle figure.As can be seen from Figure 11 by change fluorescence viologen derivative and to electrode substance concentration, the type of solvent with
And the size of voltage can regulate and control the colour developing situation of the electrochromic device.And the test of such as Figure 12 finds that No. 1 of acquisition is glimmering
The electrochromic device coloring voltage of light viologen derivative is low, and Coloring Time is short, is 0.2s, transmitance difference is high, and performance is steady
Fixed, cycle-index can reach 300 times or more, also have a good discoloration, device technology of preparing can large-scale popularization, be suitable for
The fields such as photo chromic glass and display.
In short, the above embodiment of the present invention includes a kind of Multifunction fluorescent viologen derivative, it is prepared and application, utilization are molten
The hot method of agent is prepared for a series of quick visualization solvent identifications, alkaline section pH value, temperature, NH3The quick spirit of equal alkaline gas
The fluorescence viologen derivative of quick discoloration detection.The synthetic method of line fluorescent viologen derivative of the present invention is simple simultaneously, and yield is high,
At low cost, fluorescence is strong；The preparation process of purpurine test paper is simply operable；Purpurine electrochromic device discoloration and stable circulation
Property it is good, coloring voltage is low, and discoloration is fast, easy to assembly.Fluorescence viologen derivative can show differentiation in different organic solvents
Color and fluorescence radiation variation, to achieve the effect that detection and distinguish organic solvent.And it is the above embodiment of the present invention is new
Type fluorescence viologen derivative is prepared into Test paper, remains detectability when solution state, in different alkaline sections
PH, temperature, NH3Under equal alkaline gas and organic solvent environment, test paper can show that different color changes and be passed to reach
The effect of sense detection identification.The test of purpurine electrochromic device then show fluorescence viologen derivative in electrochomeric glass and
The fields such as display have good potential using value.Above-described embodiment is adopted using fluorescence viologen derivative as fluorescent material
With the preparation method of the viologen derivative of multi-functional detection sensing, especially vinyl viologen derivative and its application field.This
Invention further relates to the preparation of purpurine colorimetric sensing test paper and electrochromic device.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, replacement, combination or the simplification made, should be equivalent substitute mode, as long as meeting the goal of the invention of the present invention,
Without departing from fluorescence viologen derivative of the present invention and its technical principle and inventive concept of application and preparation method, this is belonged to
The protection domain of invention.
Claims (10)
1. a kind of fluorescence viologen derivative, which is characterized in that molecular formula is as follows：
Wherein, A is 5~10 unit's heteroaryls optionally R 5~10 yuan of aryl replaced or optionally replaced by R；B is optionally to be taken by R
5~10 yuan of aryl in generation or 5~10 unit's heteroaryls optionally replaced by R；5~10 yuan of aryl refer to aromatic monocyclic or
And ring substituents, ring atom number are any one atomicity in 5~10,5~10 unit's heteroaryl refers to armaticity list
Ring, loop coil or simultaneously ring substituents, ring atom number are any one atomicity in 5~10, and wherein at least having 1~3 is
Hetero atom selected from N, O or S, wherein nitrogen-atoms be it is substituted or unsubstituted, L be singly-bound andR be selected from H, F,
Cl、Br、I、CN、NO2、OH、NH2、C1-6Alkyl, OC1-6Alkyl, NH (C1-6Alkyl) or N (C1-6Alkyl) (C1-6Alkyl), it is described
C1-6Alkyl, OC1-6Alkyl, NH (C1-6Alkyl), N (C1-6Alkyl) (C1-6Alkyl) optionally replaced by F, Cl, Br or I；X is halogen
Prime element.
2. fluorescence viologen derivative according to claim 1, it is characterised in that：N, O on the ring of 5~10 yuan of aryl or
The hetero atom of S, nitrogen or sulfur heteroatom are optionally aoxidized；5~10 yuan of aryl are phenyl or naphthyl；5~10 yuan of heteroaryls
Base be pyrrole radicals, pyrazolyl, imidazole radicals, oxazolyls, triazolyl, tetrazole radical, isoxazolyls, thiazolyl, furyl, thienyl,
Pyridyl group, pyrazinyl, pyrimidine radicals, benzothiazolyl, purine radicals, benzimidazolyl, indyl, isoquinolyl, quinoxalinyl, quinoline
Quinoline base, pyrazinyl, purine radicals or phenyl Bing oxazolyls.
3. fluorescence viologen derivative according to claim 1 or claim 2, which is characterized in that molecular formula is as follows：
X is F, Cl, Br or I.
4. fluorescence viologen derivative according to claim 3, which is characterized in that molecular formula is as follows：
Wherein, R1、R2、R3、R4、R5、R6、R7And R8Separately it is selected from H, F, Cl, Br, I, CN, NO2、OH、NH2、C1-6Alkyl,
OC1-6Alkyl, NH (C1-6Alkyl) or N (C1-6Alkyl) (C1-6Alkyl), the C1-6Alkyl, OC1-6Alkyl, NH (C1-6Alkyl), N
(C1-6Alkyl) (C1-6Alkyl) optionally replaced by F, Cl, Br or I, X F, Cl, Br or I.
5. fluorescence viologen derivative according to claim 4, which is characterized in that molecular formula is as follows：
6. the application of fluorescence viologen derivative described in a kind of claim 1, it is characterised in that：Using fluorescence viologen derivative as glimmering
Optical function material is applied in solvent colour developing recognition methods or gas colour developing recognition methods, or fluorescence viologen derivative is made
For the functional material of sensor, or using fluorescence viologen derivative as the functional material of electrochromic device.
7. the application of fluorescence viologen derivative according to claim 6, it is characterised in that：It can be to the liquid basified section of fluid
PH, fluid temperature (F.T.) or alkaline gas NH3The difference of concentration carries out the developing response for having differentiation, or is had under different voltages
The developing response of differentiation realizes electrochromism function.
8. the application of fluorescence viologen derivative according to claim 6, it is characterised in that：Fluorescence viologen derivative is carried on
On neutral paper material, Test paper is made；Or using fluorescence viologen derivative as electrochromism functional layer material, electricity is made
The electrochromism functional layer module of mutagens color device, electrochromic device includes electrolyte and its container, and the electrolyte includes
Electrolyte, to electrode substance and cathode substance, using fluorescence viologen derivative as the cathode substance.
9. the preparation method of fluorescence viologen derivative described in a kind of claim 1, which is characterized in that include the following steps：
(1) bis- (4- pyridines) ethylene of 1,2- and halo acetophenone derivative are weighed as reactant, or weighs 1, bis- (the 4- pyrroles of 2-
Pyridine) ethylene and benzoic acid derivative be as reactant；By the quality of 1,2- bis- (4- pyridines) ethylene and halo acetophenone derivative
Proportioning is 1:2~1:4 ratio, or it is 1 to press bis- (4- pyridines) ethylene of 1,2- and the quality proportioning of benzoic acid derivative:2~
1:4 ratio, reactant is placed in reaction vessel, and anhydrous DMF, acetonitrile or acetone solvent are then added into reaction vessel
So that reactant is fully dissolved, obtain material system mixture solution, then by above-mentioned raw materials system mixture solution 80
1~48h of back flow reaction is carried out at~140 DEG C, light yellow or yellow sediment is made to generate, and is formed containing precipitation product
Mixed liquor；
(2) it waits for being cooled to room temperature after reaction for the step (1), the mixed liquor containing precipitation product is carried out at centrifugation
Reason, isolated sediment anhydrous DMF and acetone are washed 3~6 times respectively, until the supernatant after centrifugation becomes from brown
It is colourless, 4~12h is dried under vacuum and at a temperature of 60~80 DEG C in isolated solid substance, is obtained light
Yellow, yellow, yellowish-brown, bronzing or pale powder, to obtain ethylene benzyl viologen, as fluorescence viologen derivative.
10. the preparation method of fluorescence viologen derivative according to claim 9, it is characterised in that：In the step (1),
Halo acetophenone derivative using 2- chloro-acetophenones, 2- how bromide methyl ketone, 3,4- dihydroxy -2 '-chloro-acetophenone or alpha-chloro -
3,4- dichloroacetophenones；Or the benzoic acid derivative uses 4- (2- acetyl bromides) benzoic acid.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456309A (en) * | 2018-11-22 | 2019-03-12 | 北京工业大学 | A kind of more pyrazoles nitrogen-containing heterocycle compounds and its preparation and application |
| CN111471455A (en) * | 2020-05-18 | 2020-07-31 | 上海大学 | Preparation method and application of acetophenone and derivative substituted thiazolyl viologen strong fluorescence color-changing material |
| CN112519444A (en) * | 2020-11-14 | 2021-03-19 | 西北农林科技大学 | Application of benzothiazole derivative in anti-counterfeiting and food detection |
| CN114890956A (en) * | 2022-05-10 | 2022-08-12 | 华南理工大学 | Electroluminescent material containing phenazine structure and preparation method and application thereof |
| CN114907416A (en) * | 2022-05-17 | 2022-08-16 | 西安交通大学 | Selenium-containing viologen pendant coordination metal macrocyclic supramolecules and synthesis method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3583870A (en) * | 1968-11-15 | 1971-06-08 | Eastman Kodak Co | Emulsions containing a bipyridinium salt and a dye |
| CN104860875A (en) * | 2015-05-14 | 2015-08-26 | 上海大学 | Substituent acetophenone group purpurine derivative of high-sensitivity color changing material and synthetic method thereof |
| CN106432061A (en) * | 2016-06-12 | 2017-02-22 | 上海大学 | High sensitivity color-changing acetophenone substituent viologen compound and synthesis method thereof |
| CN107417596A (en) * | 2017-05-22 | 2017-12-01 | 上海大学 | Naphthalene acetyl viologen compound and its synthetic method and application |
| CN107513035A (en) * | 2017-05-24 | 2017-12-26 | 上海大学 | 3,4 difluoro acetophenones substitution viologen compound and its preparation method and application |
-
2018
- 2018-03-09 CN CN201810193249.7A patent/CN108373444A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3583870A (en) * | 1968-11-15 | 1971-06-08 | Eastman Kodak Co | Emulsions containing a bipyridinium salt and a dye |
| CN104860875A (en) * | 2015-05-14 | 2015-08-26 | 上海大学 | Substituent acetophenone group purpurine derivative of high-sensitivity color changing material and synthetic method thereof |
| CN106432061A (en) * | 2016-06-12 | 2017-02-22 | 上海大学 | High sensitivity color-changing acetophenone substituent viologen compound and synthesis method thereof |
| CN107417596A (en) * | 2017-05-22 | 2017-12-01 | 上海大学 | Naphthalene acetyl viologen compound and its synthetic method and application |
| CN107513035A (en) * | 2017-05-24 | 2017-12-26 | 上海大学 | 3,4 difluoro acetophenones substitution viologen compound and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| -: "CAS号2086268-53-1等", 《STN REGISTRY》 * |
| A. ROTARU ET AL.: "Activité antimicrobienne in vitro de nouveaux sels diquaternaires dérivés de la 4,4’-bipyridine", 《ANN. PHARM. FR.》 * |
| ALEXANDRU V. ROTARU ET AL.: "Synthesis of New Non-Symmetrical Substituted 7,7"-Bisindolizines by the Direct Reaction of 4,4"-Bipyridinium-Ylides with Dimethyl Acetylenedicarboxylate", 《J. HETEROCYCLIC CHEM.》 * |
| MEILING HU ET AL.: "Phenolacetyl Viologen as Multifunctional Chromic Material for Fast and Reversible Sensor of Solvents, Base, Temperature, Metal Ions, NH3 Vapor, and Grind in Solution and Solid State", 《ACS OMEGA》 * |
| WEI SHI ET AL.: "High Sensitivity Viologen for a Facile and Versatile Sensor of Base and Solvent Polarity in Solution and Solid State in Air Atmosphere", 《ACS APPL. MATER. INTERFACES》 * |
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|---|---|---|---|---|
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| CN109456309B (en) * | 2018-11-22 | 2020-11-27 | 北京工业大学 | Multi-pyrazole nitrogen-containing heterocyclic compound and preparation and application thereof |
| CN111471455A (en) * | 2020-05-18 | 2020-07-31 | 上海大学 | Preparation method and application of acetophenone and derivative substituted thiazolyl viologen strong fluorescence color-changing material |
| CN111471455B (en) * | 2020-05-18 | 2022-10-11 | 上海大学 | Preparation method and application of acetophenone and derivative-substituted thiazolyl viologen high-fluorescence photochromic material |
| CN112519444A (en) * | 2020-11-14 | 2021-03-19 | 西北农林科技大学 | Application of benzothiazole derivative in anti-counterfeiting and food detection |
| CN112519444B (en) * | 2020-11-14 | 2022-04-15 | 西北农林科技大学 | Application of benzothiazole derivative in anti-counterfeiting and food detection |
| CN114890956A (en) * | 2022-05-10 | 2022-08-12 | 华南理工大学 | Electroluminescent material containing phenazine structure and preparation method and application thereof |
| CN114890956B (en) * | 2022-05-10 | 2024-01-23 | 华南理工大学 | Electroluminescent material containing phenazine structure, and preparation method and application thereof |
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