阅读说明：本技术 紫精衍生物、其制备方法与电致变色器件 (Viologen derivative, preparation method and electrochromic device ) 是由 徐春叶 施雨辰 郑建明 于 2018-05-09 设计创作，主要内容包括：本发明提供了紫精衍生物,同时提供了紫精衍生物的制备方法；本发明还提供了一种电致变色器件,其包括电解液,所述电解液中包括紫精衍生物和对电极材料。本申请利用Suzuki偶联反应在原本的4,4-联吡啶中间引入苯环、萘环或苯并噻二唑环,增大了原有紫精结构的共轭程度,改变了紫精π电子骨架的电子轨道分布,增强了其荧光性能,获得了一系列具有不同光学性能的分子；该紫精衍生物用于电致变色器件,具有较好的电致变色性能。(The present invention provides viologen derivatives, while providing the preparation method of viologen derivative；The present invention also provides a kind of electrochromic devices comprising electrolyte includes viologen derivative and to electrode material in the electrolyte.The application is using Suzuki coupling reaction the 4 of script, phenyl ring, naphthalene nucleus or diazosulfide ring are introduced among 4- bipyridyl, increase the conjugated degree of original purpurine structure, change the electron orbit distribution of purpurine pi-electron skeleton, its fluorescence property is enhanced, a series of molecules with different optical properties are obtained；The viologen derivative is used for electrochromic device, has preferable electrochromic property.)

1. a kind of viologen derivative as shown in formula (I 1), formula (I 2) or formula (I 3)；

Wherein, R₁、R₂And R₃The alkyl of the independent alkyl selected from the C1~C5 replaced or unsubstituted C1~C5.

2. viologen derivative according to claim 1, which is characterized in that the R₁、R₂And R₃It is independent selected from unsubstituted The alkyl of C1~C5.

3. viologen derivative according to claim 1, which is characterized in that the viologen derivative such as formula (I 1 '), formula (I 2 ') or formula (I 3 ') shown in；

4. a kind of preparation method of the viologen derivative as shown in formula (I 1), comprising the following steps:

A 4- pyridine boronic acid, the compound with formula (I 11) structure are reacted under the effect of the catalyst), obtained with formula (I 12) initial reactant of structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 13) structure, obtains tying with formula (I 14) The presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtain the purple as shown in formula (I 1) Smart derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₁The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

5. a kind of preparation method of the viologen derivative as shown in formula (I 2), comprising the following steps:

A) 4- pyridine boronic acid is reacted under the effect of the catalyst with the compound with formula (I 21) structure, is obtained with formula (I 22) initial reactant of structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 23) structure, obtains tying with formula (I 24) The presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtain the purpurine as shown in (I 2) Derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₂The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

6. a kind of preparation method of the viologen derivative as shown in formula (I 3), comprising the following steps:

A) 4- pyridine boronic acid is reacted under the effect of the catalyst with the compound with formula (I 31) structure, is obtained with formula (I 32) initial reactant of structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 33) structure, obtains tying with formula (I 34) The presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtain the purpurine as shown in (I 3) Derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₃The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

7. the preparation method according to claim 4, which is characterized in that the catalyst is tetra-triphenylphosphine palladium, step A) The reaction is carried out in the in the mixed solvent of titanium dioxide ring and water；The compound containing hexafluoro-phosphate radical is lithium hexafluoro phosphate Or ammonium hexafluorophosphate.

8. preparation method according to claim 5, which is characterized in that the catalyst is three (dibenzylidene Asia ketone) two Palladium, step A) it is described reaction the in the mixed solvent of dioxane and water carry out；The compound containing hexafluoro-phosphate radical is Lithium hexafluoro phosphate or ammonium hexafluorophosphate.

9. preparation method according to claim 6, which is characterized in that the catalyst is tetra-triphenylphosphine palladium, step A) The reaction is carried out in n,N-Dimethylformamide and the in the mixed solvent of water；The compound containing hexafluoro-phosphate radical is six Lithium fluophosphate or ammonium hexafluorophosphate.

10. a kind of electrochromic device, including electrolyte, which is characterized in that include viologen derivative and right in the electrolyte Electrode material, the viologen derivative are described in viologen derivative described in claims 1 to 3 or any one of claim 4~9 Preparation method prepared by viologen derivative.

Technical field

The present invention relates to electrochromic display device (ECD) field more particularly to viologen derivatives, preparation method and electrochromism Device.

Background technique

Electrochromism is that the optical properties (reflectivity, transmitance, absorptivity etc.) of material are sent out under the action of extra electric field The phenomenon that giving birth to stable, reversible color change, shows as the reversible change of color and transparency in appearance.Electrochromic material As a kind of very promising new function material, in large-scale display, optoelectronic switch, electrochromism memory device, building The fields such as glass pane and its smart windows all have wide practical use.

Electrochromic material ratio need to have good ion and electron conduction, higher contrast, discoloration efficiency and Cycle period performance.Electrochromic material is broadly divided into inorganic electrochromic material and organic electrochromic material.Inorganic electroluminescence Off-color material is mainly with WO₃Equal transition-metal oxides are representative, these transition metal oxides pass through ion and electronics Injection and altogether extraction altogether, make its chemical valence state or crystal structure change, to realize the reversible process of coloring and colour fading；Have Machine electrochromic material mainly using purpurine etc. has the molecule of conjugated system as representative, be the oxidation that is occurred by electron exchange also Original reacts the reversible change to realize coloring and colour fading comprising small organic molecule, such as purpurine；Metal coordination complex, such as phthalein Change cyanines；Organic conductive polymer, such as polyaniline, polypyrrole or polythiophene.

Purpurine (N, N- and replace -4,4- bipyridyl) class material in organic electrochromic material is since discovery in 1932 years Extensive research is received in electrochromism field.Viologen molecules have quite outstanding electrochromic property, are prepared based on purpurine Electrochromic device have big advantage in display technology.But the research done at present to viologen molecules is only limitted to N, N- bis- The change of substituent group, this makes purpurine material be difficult to meet the Research Requirements of multifunction.

Summary of the invention

Present invention solves the technical problem that being to provide a kind of viologen derivative, viologen derivative provided by the present application makes electricity Mutagens color device has preferable electrochromic property.

In view of this, this application provides one kind viologen derivatives as shown in formula (I 1), formula (I 2) or formula (I 3)；

Wherein, R₁、R₂And R₃The alkyl of the independent alkyl selected from the C1~C5 replaced or unsubstituted C1~C5.

Preferably, the R₁、R₂And R₃The independent alkyl selected from unsubstituted C1~C5.

Preferably, shown in the viologen derivative such as formula (I 1 '), formula (I 2 ') or formula (I 3 ')；

Present invention also provides the preparation methods of one kind viologen derivative as shown in formula (I 1), comprising the following steps:

A 4- pyridine boronic acid, the compound with formula (I 11) structure are reacted under the effect of the catalyst), obtained with formula The initial reactant of (I 12) structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 13) structure, is obtained with formula (I 14) presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtained as shown in formula (I 1) Viologen derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₁The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

Present invention also provides the preparation methods of one kind viologen derivative as shown in formula (I 2), comprising the following steps:

A) 4- pyridine boronic acid is reacted under the effect of the catalyst with the compound with formula (I 21) structure, is had The initial reactant of formula (I 22) structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 23) structure, is obtained with formula (I 24) presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtained as shown in (I 2) Viologen derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₂The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

Present invention also provides the preparation methods of one kind viologen derivative as shown in formula (I 3), comprising the following steps:

A) 4- pyridine boronic acid is reacted under the effect of the catalyst with the compound with formula (I 31) structure, is had The initial reactant of formula (I 32) structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 33) structure, is obtained with formula (I 34) presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtained as shown in (I 3) Viologen derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₃The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

Preferably, the catalyst be tetra-triphenylphosphine palladium, step A) it is described reaction titanium dioxide ring and water mixing it is molten It is carried out in agent；The compound containing hexafluoro-phosphate radical is lithium hexafluoro phosphate or ammonium hexafluorophosphate.

Preferably, the catalyst be three (dibenzylidene Asia ketone) two palladiums, step A) it is described reaction in dioxane and water In the mixed solvent carry out；The compound containing hexafluoro-phosphate radical is lithium hexafluoro phosphate or ammonium hexafluorophosphate.

Preferably, the catalyst be tetra-triphenylphosphine palladium, step A) it is described reaction in n,N-Dimethylformamide and water In the mixed solvent carry out；The compound containing hexafluoro-phosphate radical is lithium hexafluoro phosphate or ammonium hexafluorophosphate.

It include viologen derivative in the electrolyte present invention also provides a kind of electrochromic device, including electrolyte With to electrode material, the viologen derivative is preparation method described in viologen derivative described in above scheme or above scheme Prepared viologen derivative.

This application provides a kind of viologen derivative, be using coupling reaction by phenyl ring, naphthalene nucleus with or diazosulfide Ring is introduced among two pyridine rings in viologen molecules, increases the conjugated degree of viologen molecules, changes purpurine pi-electron bone The electron orbit of frame is distributed, and enhances its fluorescence property, so that the electrochromic device of viologen derivative preparation is with high Optical modulation rate, changeable coloured state color, the cyclical stability of overlength and stable fluorescent emission phenomenon.

Detailed description of the invention

Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of compound prepared by embodiment 1；

Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of compound prepared by embodiment 2；

Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of compound prepared by embodiment 3；

Fig. 4 is electrochromic device structural schematic diagram of the present invention；

Fig. 5 is the electrochromism property curve graph of viologen derivative provided by the invention；

Fig. 6 is fluorescence spectrum and the corresponding fluorescence photo of electrochromic device provided by the invention；

Fig. 7 is the cyclical stability curve graph of electrochromic device provided by the present application.

Specific embodiment

For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.

For the status of present electrochromic device, in order to expand the multifunction of purpurine material, the embodiment of the present invention is public Viologen derivative is opened, viologen derivative provided by the present application has obtained having electroluminescent change by the molecular structure of change purpurine The difunctional viologen derivative of color and fluorescence, using the material preparation electrochromic device have high optical modulation rate, The cyclical stability of changeable coloured state color, overlength and stable fluorescent emission phenomenon；Specifically, herein described purpurine Shown in the structure of derivative such as formula (I 1), formula (I 2) or formula (I 3):

Wherein, R₁、R₂And R₃The alkyl of the independent alkyl selected from the C1~C5 replaced or unsubstituted C1~C5.

More specifically, the R₁、R₂And R₃The independent alkyl selected from unsubstituted C1~C5；More specifically, described such as formula In viologen derivative shown in (I 1), the R₁Selected from methyl；In the viologen derivative as shown in formula (I 2), the R₂Choosing From methyl；In the viologen derivative as shown in formula (I 3), the R₂Selected from butyl；In these cases, the purpurine is spread out Shown in biology such as formula (I 1 '), formula (I 2 ') or formula (I 3 ')；Wherein the viologen derivative as shown in (I 1 ') may be simply referred to as PV, and such as (I 2 ') shown in viologen derivative may be simply referred to as NV, the viologen derivative as shown in (I 3 ') may be simply referred to as BV.

The present invention also provides the preparation methods of the viologen derivative, specific:

The preparation method of the viologen derivative as shown in (I 1), comprising the following steps:

A 4- pyridine boronic acid, the compound with formula (I 11) structure are reacted under the effect of the catalyst), obtained with formula The initial reactant of (I 12) structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 13) structure, is obtained with formula (I 14) presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtained as shown in (I 1) Viologen derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₁The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

In above-mentioned preparation in the viologen derivative as shown in formula (I 1), first by 4- pyridine boronic acid, with formula (I 11) structure Compound react under the effect of the catalyst, obtain the initial reactant with formula (I 12) structure；It is above-mentioned initial anti-preparing During answering object, specifically by 4- pyridine boronic acid, compound, potassium carbonate and catalyst with formula (I 11) structure in solvent Middle hybrid reaction, results in initial reactant.In above process, the catalyst is tetra-triphenylphosphine palladium, described molten Agent is the mixed solvent of dioxane and water.

After obtaining initial reactant, by the initial reactant with the compound with formula (I 13) structure in solvent Middle reaction obtains the presoma with formula (I 14) structure；The solvent preferably uses chloroform.

Presoma obtained above and the compound containing hexafluoro-phosphate radical are finally subjected to anion exchange, had There is viologen derivative shown in formula (I 1).In this application, the compound containing hexafluoro-phosphate radical is selected from lithium hexafluoro phosphate Or ammonium hexafluorophosphate.

Present invention also provides the preparation methods of the viologen derivative as shown in formula (I 2), comprising the following steps:

A) 4- pyridine boronic acid is reacted under the effect of the catalyst with the compound with formula (I 21) structure, is had The initial reactant of formula (I 22) structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 23) structure, is obtained with formula (I 24) presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtained as shown in (I 2) Viologen derivative；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₂The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

During viologen derivative of the above-mentioned preparation as described in formula (I 2), equally it is divided into the preparation-of initial reactant Preparation-viologen derivative preparation of presoma, in above three step, the preparation of presoma and the preparation of viologen derivative Process is identical as the preparation process of viologen derivative as described in formula (I 1), and difference is only that in the selection of raw material, therefore herein Place is without repeating.

In the preparation process for preparing initial reactant, 4- pyridine boronic acid and the compound with formula (I 21) structure are existed It is reacted under the action of catalyst, obtains the initial reactant with formula (I 22) structure；Specifically, by 4- pyridine boronic acid, potassium phosphate It mixes with the compound with formula (I 21) structure, then is mixed with dissolved with tricyclohexyl phosphine with the organic solvent of catalyst, instead It answers, obtains initial reactant；Above-mentioned organic solvent is dioxane and water, and the catalyst is selected from three (dibenzylidene Asia ketone) two Palladium.

Present invention also provides the preparation methods of one kind viologen derivative as shown in formula (I 3), comprising the following steps:

A) 4- pyridine boronic acid is reacted under the effect of the catalyst with the compound with formula (I 31) structure, is had The initial reactant of formula (I 32) structure；

B) initial reactant is reacted in a solvent with the compound with formula (I 33) structure, is obtained with formula (I 34) presoma of structure；

C the presoma and the compound containing hexafluoro-phosphate radical) are subjected to anion exchange, obtained as shown in (I 3) Viologen derivative；

R₃-X₂(Ⅰ33)；

Wherein, X₁And X₂It is independent to be selected from halogen；

R₃The alkyl of alkyl or unsubstituted C1~C5 selected from substituted C1~C5.

During viologen derivative of the above-mentioned preparation as described in formula (I 3), equally it is divided into the preparation-of initial reactant Preparation-viologen derivative preparation of presoma, in above three step, the preparation of presoma and the preparation of viologen derivative Process is identical as the preparation process of viologen derivative as described in formula (I 1), and difference is only that in the selection of raw material, therefore herein Place is without repeating.

Preparation for initial reactant, the application are urging 4- pyridine boronic acid and the compound with formula (I 31) structure It is reacted under the action of agent, obtains the initial reactant with formula (I 32) structure；In the above-mentioned process for preparing initial reactant In, in order to react sufficiently, then will have compound, 4- pyridine boronic acid, potassium carbonate and the catalyst of formula (I 31) structure organic molten Hybrid reaction in agent, obtains initial reactant.The catalyst is tetra-triphenylphosphine palladium, and the organic solvent is N, N- dimethyl The mixed solvent of formamide and water.

Phenyl ring, naphthalene nucleus and diazosulfide ring are introduced in viologen molecules by the application by Suzuki coupling reaction In two pyridine rings, the conjugated degree of viologen molecules is increased, then with the nitrogen-atoms on alkyl modified pyridine ring, result in A series of viologen derivatives with different electrochromic properties.

The present invention also provides application of the viologen derivative in electrochromic device, specifically, the present invention also mentions A kind of electrochromic device is supplied comprising electrolyte includes viologen derivative and ferrocene, the purpurine in the electrolyte Derivative is viologen derivative described in above scheme.

The preparation process of above-mentioned electrochromic device is carried out according to mode well known to those skilled in the art, specifically, will Viologen derivative dissolves in the interlayer being poured among two plate bases in the electrolytic solution with to electrode material ferrocene, then with purple Outer glue encapsulates entire device, and the structure of electrochromic device described herein is as shown in Figure 4.Electrochromism provided by the present application The working principle of device specifically: when external circuitry connect when, viologen derivative under the action of electric field to movable cathode, in yin The form that electron reduction is radical cation is obtained on tin indium oxide (ITO) electro-conductive glass of pole, which shows deeper Color, device is in coloured state at this time；When external circuitry disconnects, the viologen derivative radical cation in coloured state Molecule free diffusing restores original colorless and transparent state into solution and with charge-exchange is carried out to electrode material, at this time device In colour fading state.

The present invention for the first time by the aromatic rings such as benzene, naphthalene and diazosulfide be introduced into classical small organic molecule purpurine (N, N- bis- replaces -4,4- bipyridyl) in, and it is made into based on these materials the electrochromic device of sandwich structure, it obtains Completely new electrochromism-fluorescent dual-function device.These New-type bifunctional electrochromic devices have extremely outstanding electroluminescent change Color performance, three kinds of viologen derivative devices based on phenyl ring, naphthalene nucleus and diazosulfide ring respectively in 512nm, 544nm and There is greatest optical modulation rate at 594nm, 76.9%, 74.1% and 69.0% can be reached respectively, corresponding device coloured state Color is pink, aubergine and bluish violet respectively, as shown in Figure 5；In addition to electrochromism property, spread out based on these purpurines The device of biomaterial can launch the fluorescence of high-intensitive different colours under the excitation of ultraviolet source, as shown in fig. 6, three The fluorescence of material shows blue, two kinds of fluorescence colors of sapphirine under ultraviolet excitation irradiation respectively.At the same time, device exists Cycle life under corresponding greatest optical transmitance wavelength can reach 1,000 times, as shown in Figure 7.

For a further understanding of the present invention, below with reference to embodiment to viologen derivative provided by the invention, its preparation side Method is described in detail with application, and protection scope of the present invention is not limited by the following examples.

Raw material in following embodiment is commercial product.