阅读说明：本技术 一种紫精类化合物、制备方法及其用途 (Viologen compound, preparation method and application thereof ) 是由 闫江琳 唐果东 戴静 张宇 朱安峰 支三军 李康 于 2019-10-21 设计创作，主要内容包括：本发明涉及一种非对称结构的紫精类化合物、制备方法及其用途,属于光致变材料技术领域。本发明提供的化合物具有如下式所示的结构：<Image he="127" wi="419" file="RE-DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>荧光发射光谱图和相应的荧光数据表明,引入乙酰联苯基,能够使得化合物的最大发射波长产生红移,荧光强度大大加强,可归因于接入的乙酰联苯基上的羰基和苯环的相互作用,使得电子云密度增加,π电子离域性提高,荧光波长红移,荧光强度增强。以同时引入乙烯基和乙酰联苯基时,荧光强度最大。该化合物具有较快的响应时间、更高的紫外和荧光强度,以及更好的稳定性和循环使用性能。(The invention relates to a viologen compound with an asymmetric structure, a preparation method and application thereof, belonging to the technical field of photochromic materials. The compound provided by the invention has a structure shown as the following formula: the fluorescence emission spectrogram and corresponding fluorescence data show that the maximum emission wavelength of the compound can generate red shift by introducing the acetylbiphenyl, the fluorescence intensity is greatly enhanced, and the interaction between carbonyl and a benzene ring on the accessed acetylbiphenyl can be attributed to, so that the electron cloud density is increased, the pi electron delocalization is improved, the fluorescence wavelength is red shifted, and the fluorescence intensity is enhanced. To be provided withWhen vinyl and acetylbiphenyl groups are simultaneously introduced, the fluorescence intensity is maximized. The compound has the advantages of fast response time, higher ultraviolet and fluorescence intensity, and better stability and recycling performance.)

1. A viologen compound is characterized by having any one of the following structures:

（2a-1）；

2. the method for preparing the viologen compound as claimed in claim 1, which comprises the following steps:

preparation of Compound (A):

preparation of Compound (B):

preparation of Compound (C):

preparation of Compound (D):

preparation of Compound (1 a-1):

preparation of Compound (1 a-2):

preparation of Compound (2 a-1):

preparation of Compound (3 a-1):

。

3. use of the viologen-based compound of claim 1 in a photochromic device.

4. The application of the group shown in the formula (I) in improving the absorption coefficient of a viologen compound or red-shifting the absorption wavelength or cycling response performance;

（I）。

5. use according to claim 4, wherein in one embodiment the absorption coefficient is in the ultraviolet or visible range.

6. Use of a group of formula (I I) for increasing the absorption coefficient of a viologen-based compound or red-shifting the absorption wavelength or fluorescence intensity;

7. the use of the viologen compound of claim 1 in the preparation of a photo-thinned film material.

Technical Field

The invention relates to a viologen compound with an asymmetric structure, a preparation method and application thereof, belonging to the technical field of photochromic materials.

Background

In 1932, Michaelis et al discovered that 1,1 '-dimethyl-4, 4' -bipyridinium salt turned purple in its reduced state, and attracted much interest, and so called "viologen", which has a general structural formula shown below.

The structural formula of the viologen ion is shown as follows.

Later, 4' -bipyridinium salts were collectively called viologens, and these materials had reversible oxidation-reduction properties and had large variations in the absorption coefficients of visible light at different wavelengths in the oxidation state and the reduction state. The viologen compound has structure modifiability, and can be connected with different groups to display different colors. The viologen compound is a cationic compound, and has many researches and applications in the aspects of biology, electrochemistry and the like due to unique oxidation-reduction property, such as an electron transfer catalyst, an electrochromic or photochromic material, an electrode modification material and the like.

The viologen compound is a redox type organic micromolecule color-changing material, has excellent electrochemical performance and electrical activity, and the N atom on the pyridine ring as a precursor loses electrons to form quaternary ammonium salt cations, and has a pi conjugated structure, so that the formed cations have excellent electrochromic property. The viologen compounds have three oxidation-reduction states, and the conversion relation between the three oxidation-reduction states is shown as a formula (III).

Since 1973, researchers such as Schoot C J and the like synthesized viologen electrochromic materials for memory display, and the electrochromic materials formally entered the organic field. BF 4-is adopted by Sung Hong Kim and Jin Seok Bae and the like as anion to synthesize the micromolecule viologen [1 ] with double-node substituent]Two viologen micromolecules are connected into a system by dihalogenated hydrocarbon to obtain an electrochromic system with five redox states, a solution type electrochromic device is assembled, two-color development of blue and mauve is realized under different voltages, and the influence of the length of an alkyl chain and the size of anions on the color of a viologen compound is discussed. Sun-ah Park and Heung Cho Ko et al introduced pyrrole into viologen molecules and polymerized by electrochemical polymerization to synthesize side chain viologen derivatives with polypyrrole as the main chain, and studied their cyclic voltammetric properties [2]. Then, thiophene groups are introduced into viologen molecules in the same way to synthesize side chain type viologen derivatives taking polythiophene as a main chain, and meanwhile, multicolor color development of polythiophene and viologen is realized, however, polythiophene is easy to decompose due to poor stability and poor circulation effect. Sun-ah et al, by improving the molecular structure, polymerize thiophene moieties into polymer conductors and introduce viologen into the polymer conductors to synthesize derivatives, which have good cycling effects [3]. Joge Garcia-Canads and Francisco Fabregat-Santiago [4]And the researchers find that the titanium dioxide and the adsorbed viologen have faster interface electron transfer capacity, and study the charge transfer between the electrode and the viologen molecule for the first time. Jook Woopark et al, complexed with cyclodextrin and viologen compounds, studied the structures of two isomeric pseudorotaxanes and reducing radicals formed [5,6]In the next few years, the kinetic and thermodynamic direction of formation of isomeric pseudorotaxanes has been further investigated. Viologen modified mesoporous nano crystal anatase electrode for Sun Yeun Choi and the likeThe electrochromic performance is researched, and the great contact area of ordered pore structure, nano crystal anatase wall structure and anchoring viologen is found to enhance the electrochromic performance [7]. Martin Moller, Lorenz Walder et al anchored viologen to TiO via a cascade type cross-linking reaction₂Switchable electrochromic images have been reported on electrodes, in combination with inkjet printing techniques [8]。Mercedes Alvaro、Hermenegildo Garcia[9]The optical properties of viologen and single-walled carbon nanotubes were studied by et al. Subsequently, Wonjoo Lee, Whikun Yi [10]The photocurrent of the photoelectrochemical cell of the viologen-ruthenium compound is increased by using the single-walled carbon nanotube and the terminal carboxylic acid group as an electron transfer bridge, and the single-walled carbon nanotube is researched to be in the following 11,12]The role played in the reaction was concluded that it inhibited the rearrangement reaction. Tarek Abou Elmaaty, Lyle w. castle investigated a novel synthesis method for regioselectively controlling 1,1 '-dioctyl-4, 4' -bipyridine as an electron transfer agent in the synthesis of trialkyl-substituted pyrazines by reacting alpha-nitroketones with alpha-aminoketones. Giuseppe Chidichimo et al prepared solid thermoplastic electrochromic film by using polyethylene, polypropylene carbonate, ethyl viologen and the like, and made a solid electrochromic device [13 ]]. Kirill Nikitin et al used the PASSY new nuclear magnetic resonance technology to study rotaxane and single electron reduction cation radical, its oxidation state structure and its supermolecule function of redox activity on the surface of solution and nano particles, and subsequently studied the redox activity of rotaxane on the surface of gold. Yoshinori Nishikitani et al attached ferrocene to viologen skeleton, studied the optical properties thereof, and made electrochromic devices [14 ]]. The Nicolas Mercier subject group reports three compounds, all of which have formate anions formed by in-situ decomposition of DMF solvent molecules, and in the process of testing the color change performance, the obtained oxygen is one of the reasons for influencing the color change speed.

[1]Sung H K,Jin S B,Seok H H.Dimer formation of viologen derivatives and their electrochromic properties.Dyes and Pigments,1997,33(2):167-172

[2]Park S,Ko H C.Assignments of cyclic voltammetric peaks during electrochemical polymerization of pyrrole with viologen pendant.SynthetiMetals,2003,139(2):439-443

[3]Ko H C,Park S.Electrochemistry and electrochromism of the polythiophene derivative with viologen pendant.Synthetic Matals,2002,132(1):15-20

[4]Garcia-Canades J,Fabregat-Santiago F.Characterisation of electrochromic viologen-modified nanocrystalline TiO2 films by frequency-resolved optional transmission spectroscopy.Electrochemistry Communications,2003,5(3):199-202

[5]Park J W,Kim J H,et al.Photosensitized Two-electro Reduction of Viologen and the Reactivity of the Neutral Viologen.1994,23(11):2075-2078

[6]Park J W,Kim J H,et al.Facile domerization of viologen radical cations covalently bonded toβ-cyclodextrin and suppression of thedimerization byβ-cyclodextrin and amphiphiles.The Journal of PhysicalChemistry,1996,100(2):769-774

[7]Choi S Y,Mamak M,Neil Coombs,et al.Electrochromic Performance of Viologen-Modified Periodic Mesoporous Nanocrystalline Anatase Electrodes.NanoLetters,2004,4(7):1231-1235

[8]Bongard D,Moller M,et al.Synthesis of Nonsymmetrucally N,N'-Diaryl-Substituted4,4'-Bipyridinium Salts with Redox-Tunable and Tianium Dioxide(TiO2)-Anchoring Properties.Helvetica,2005,88(22):3200-3209

[9]Alvaro M,Aprile C,Atienzar P,et al.Preparation and Photochemistry of Single Wall Carbon Nanotubes Having Covalently Anchored Viologen Units.TheJournal of Physical Chemistry B,2005,109(16):7692-7697

[10]Lee W,Lee J,Lee S H,et al.Improved Photocurrent in Ru(2,2'-bipyridine-4,4'-dicarboxylic acid)2(NCS)2/Di(3-aminopropyl)viologen/Single-Walled Carbon Nanotubes/Indium Tin Oxide System:Suppression of RecombinationRraction by Use of Single-Walled Carbon Nanotubes.The Journal of PhysicalChemistry C,2007,111(26):9110-9115

[11]Elmaaty T A,Castle L W.Facile Regioconlled Synthesis of Trialkyl-Substituted Pyrazines.Org.Lett,2005,7(24):5529-5530

[12] Interface assembly and structure and performance research of carbon nanotube composite based on viologen functionalization, namely Liujiang, Chenyin and Qiandojin, 2013

[13]Chidichimo G,Benedittis M De,et al.Soild Thermolastic Laminable Electrochromic Film.Chem Mater,2007,19(3):353-358

[14]Nishikitani Y,Uchida S,et al.Photo and Electrochemical Properies of linked Ferrocene and Viologen Donor-Acceptor-Type Molecules and Their App；ication to Electrochromic Devices.The Journal of Physical Chemistry C,2008,112(11):4372-4377

The viologen compound is the most representative organic micromolecule electrochromic material, has good electrochromic and photochromic performances, and can be designed and modified in molecular structure. When the viologen compound is synthesized, different substituent groups are applied to change the structure of the viologen compound, so that the color change mechanism of the viologen compound is changed, the service life of the viologen compound is prolonged, and the response time is prolonged.

Disclosure of Invention

The purpose of the invention is: provides an amethyst compound which has faster response time, higher ultraviolet and fluorescence intensity, and better stability and recycling performance.

The technical scheme is as follows:

in a first aspect of the present invention, there is provided:

a viologen compound has any one of the following structures:

in a second aspect of the present invention, there is provided:

the preparation method of the viologen compound comprises the following steps:

preparation of Compound (A):

preparation of Compound (B):

preparation of Compound (C):

preparation of Compound (D):

preparation of Compound (1 a-1):

preparation of Compound (1 a-2):

preparation of Compound (2 a-1):

preparation of Compound (3 a-1):

in a third aspect of the present invention, there is provided:

the viologen compound is applied to photochromic devices.

In a fourth aspect of the present invention, there is provided:

the application of the group shown in the formula (I) in improving the absorptivity of the viologen compound or red-shifting the absorption wavelength;

in one embodiment, the absorption coefficient is in the ultraviolet region or the visible region.

In a fifth aspect of the present invention, there is provided:

use of a group of formula (I I) for increasing the absorption coefficient of a viologen-based compound or red-shifting the absorption wavelength or fluorescence intensity;

in a sixth aspect of the present invention, there is provided:

the viologen compound is applied to preparing a photoinduced thinning film material.

In one embodiment, the use of viologen-based compounds is for reducing photofatigue or increasing the rate of discoloration of film materials.

Advantageous effects

The ultraviolet-visible spectrum and the fluorescence emission spectrum are utilized to research the spectral properties of the viologen compounds. Ultraviolet-visible spectrograms and molar absorption coefficients of the compounds at different wavelengths show that the viologen compounds have wider peaks, larger molar absorption coefficients, strong light absorption capacity and strong coloring. Viologens absorb at 270nm, due to absorption on the pyridine ring, giving a red shift compared to 4,4 '-bipyridine, due to the effect of the electronic effect of the group attached to the nitrogen atom on the 4,4' -bipyridine. When 4,4' -bipyridine is connected with acetylbiphenyl, the compound has an absorption peak at 555nm of a visible light region, green light is absorbed, and the solution is purple. The fluorescence emission spectrogram and corresponding fluorescence data show that the maximum emission wavelength of the compound can generate red shift by introducing the acetylbiphenyl, the fluorescence intensity is greatly enhanced, and the interaction between carbonyl and a benzene ring on the accessed acetylbiphenyl can be attributed to, so that the electron cloud density is increased, the pi electron delocalization is improved, the fluorescence wavelength is red shifted, and the fluorescence intensity is enhanced. So that the fluorescence intensity is maximized when vinyl groups and acetylbiphenyl groups are simultaneously introduced. The compounds B, 1a-1, 2a-1 and 3a-1 can generate photochromism under sunlight, and the higher the sunlight intensity is, the higher the photochromism speed of the compounds is.

Drawings

FIG. 1 is an infrared spectrum of Compound A

FIG. 2 is an infrared spectrum of Compound B

FIG. 3 is an IR spectrum of Compound C

FIG. 4 is an IR spectrum of Compound D

FIG. 5 is an IR spectrum of Compound 1a

FIG. 6 is an IR spectrum of Compound 2a

FIG. 7 is an IR spectrum of Compound 3a

FIG. 8 is an IR spectrum of Compound 4a

FIG. 9 is an infrared spectrum of Compound 1a-1

FIG. 10 is an infrared spectrum of compound 1a-2

FIG. 11 is an IR spectrum of Compound 2a-1

FIG. 12 is an IR spectrum of Compound 3a-1

FIG. 13 is a UV-Vis spectrum of 4,4' -bipyridine and Compound A, B, C, D

FIG. 14 is a UV-VIS spectrum of compounds 2a, B, 1a-1, 2a-1, 3a-1

FIG. 15 is a UV-VIS spectrum of the compounds 1a, 1a-1 and 1a-2

FIG. 16 UV-VIS spectra of compounds 3a and 3a-1

FIG. 17 is a color conversion chart of Compound B

FIG. 18 is a color conversion chart of Compound 1a-1

FIG. 19 is a graph showing fluorescence emission spectra of 4,4' -bipyridine and compound A, B, C, D

FIG. 20 is a fluorescence spectrum chart of the compounds 1a, 1a-1 and 1a-2

FIG. 21 is a fluorescence spectrum chart of compounds 2a, B, 1a-1, 2a-1 and 3a-1

FIG. 22 is a fluorescence spectrum of compounds 3a and 3a-1

FIG. 23 is a graph showing the change in absorbance of a photochromic film during fading

Detailed Description

Synthesis of symmetrical viologen compounds