KR100934645B1 - Photochromic diaryethene compounds capable of oxidative polymerization, diarylethene polymer compositions containing them and nanostructures containing them - Google Patents

Abstract

The present invention provides a chemical and electrochemical polymerization of a novel photochromic diarylethene compound having a photochromic property with an oxidation level of 1.8 V or less (Ag / AgCl basis) and an oxidizing agent. It relates to a diaryl ethene polymer prepared by the present invention and a nanostructure having a thin film, particles, and block shape to which the polymer is applied.

Diaryethene Compound, Polymer, Photochromic, Photopolymer, Transparency, Optical Switch

Description

Oxidatively polymerizable photochromic diarylethene compounds, composiiton of diarylethene polymers, and their nanostructures

The present invention provides a chemical and electrochemical polymerization of a novel photochromic diarylethene compound having a photochromic property with an oxidation level of 1.8 V or less (Ag / AgCl basis) and an oxidizing agent. It relates to a diaryl ethene polymer prepared by the present invention and a nanostructure having a thin film, particles, and block shape to which the polymer is applied.

Diarylethene derivatives are organic photochromic molecules, which can be discolored by light in the ultraviolet region and reversibly discolored by light in the visible region.

Irie et al. Published a method for preparing photochromic diarylethene compounds and their uses, which are known to have discoloration characteristics by UV / visible light and excellent repeatability [Masahiro Irie, Chem. Rev, 2000, 100 (5), 1685-1716. However, when applying to the device using the photochromic diaryl ethene compound, it is difficult to manufacture a thin film, and because the oxidation level is high, it is not polymerized by a general oxidation method, and the electrical conductivity of the polymerized polymer is applied to the conductive electrode because it is low. There is a problem that is difficult to use as an optical thin film.

Diaryl ethene polymers have been developed to solve this problem, and various methods of manufacturing a thin film by a solution processing method are known. As an example, the present inventor has proposed a vinyl group-containing diarylethene monomer and a method for preparing a photohalopolymer prepared by using the same [Korea Patent Publication No. 2003-25622] A solution such as spin coating a polymer having photochromic properties The method of manufacturing easily as a processing method was proposed. In addition, a method of preparing a photochromic fluorescent polymer has been invented and a method of easily preparing a polymer thin film for controlling photochromicity and fluorescence at the same time by using a solution processing method such as spin coating has been proposed [Korea Patent Publication No. 2003-85251] ].

However, the above polymers have low conductivity, which is difficult to apply to a conductive electrode to be used as a photoelectric thin film. Also, the polymer thin film has a very low photoconductivity, so that photocurrent generation in the polymer thin film is less than nanoampere (nA). .

In order to solve this problem, the present inventors use a compound represented by the following structure in which 3,4-ethylenedioxythiophene (EDOT, 3,4-ethylenedioxythiophene) group is substituted with diarylethene having photochromic properties (BTFTT). Synthesis and electrochemical properties of this compound showed that the oxidation level was lower than 1.5, so that it could be electrochemically polymerized and published in the paper [J. Lee, T. Kwon, E. Kim, "Electropolymerization of an EDOT-modified diarylethene" Tetrahedron Lett. 48 (2007) 249].

[BTFTT]

However, the BTFTT compound has a very slow photochromic property after electropolymerization and has a problem in thickness control during film production by electropolymerization.

The present invention is to improve the conventional photochromic compound is very slow photochromic properties after the electropolymerization, and to control the thickness of the thin film during the production of the thin film by the electropolymerization method, the polymerization at low voltage of 2 V or less At the same time, a thin film is formed, and a novel diarylethene compound having excellent electrochemical stability and capable of light switching is proposed. The novel compounds are excellent in photochromic properties and low in oxidation level, and thus polymers can be formed by the oxidation method, and electrochemical methods can directly electrodeposit a polymer thin film from a monomer mixture onto a conductor. Therefore, the polymer thin film prepared above generates high efficiency photocurrent and has a reversible switching characteristic, and thus it is expected to be applied as a new photoelectric material such as photoelectrode, optical sensor, solar cell, photocatalyst, photoimaging, and the like.

The present invention is characterized by the photochromic diaryl ethene compound represented by the following formula (1).

In Chemical Formula 1,

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이고,R ¹ And R ² are the same or different, and CN, Cl, Br or R ¹ C═CR ² is

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,

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ego,

또는

으로, Ar ¹ and Ar ² are the same or different,

or

to,

In this case, R ³ and R ⁴ is an alkyl group having 1 to 20 carbon atoms or an alkyleneoxy group having 1 to 20 carbon atoms, and X ¹ and X ² are the same or different, respectively -O-, -S- or -N (CH ₃ ) -Represents; The dashed line indicates the connecting portion towards the ethen as a connecting portion;

을 나타내며, 이때, R⁵ 및 R⁶은 수소, 벤젠기, 탄소수 1 내지 20의 알킬기, 탄소수 1 내지 20의 알킬에스터기, 탄소수 1 내지 20의 폴리알킬렌옥시, 탄소수 1 내지 20의 알콕시기, O-CH(R⁷)CH₂O, S-CH(R⁸)CH₂S, S-CH(R⁹)CH₂O 또는 N=CH(R¹⁰)CH=N의 치환기를 나타내고, 이들 치환기는 방향족 환의 연결부위(점선)이외의 부분에 치환되며; R⁷, R⁸, R⁹ 및 R¹⁰은 각각 수소, 탄소수 1 내지 20의 알킬, 탄소수 1 내지 20의 알킬에스터기, 탄소수 1 내지 20의 알킬렌옥시, 또는 탄소수 1 내지 20의 알콕시기이다.Ar ³ and Ar ⁴ are the same or different

Wherein R ⁵ and R ⁶ represent hydrogen, a benzene group, an alkyl group having 1 to 20 carbon atoms, an alkylester group having 1 to 20 carbon atoms, a polyalkyleneoxy having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, Substituents of O-CH (R ⁷ ) CH ₂ O, S-CH (R ⁸ ) CH ₂ S, S-CH (R ⁹ ) CH ₂ O or N = CH (R ¹⁰ ) CH = N, and these substituents Is substituted at a portion other than the linking portion (dotted line) of the aromatic ring; R ⁷ , R ⁸ , R <^9> and R <^10> is hydrogen, a C1-C20 alkyl, a C1-C20 alkylester group, a C1-C20 alkyleneoxy, or a C1-C20 alkoxy group, respectively.

In addition, the diaryl ethene homopolymer prepared by polymerizing the photochromic diaryl ethene compound: the photochromic diaryl ethene compound, ethylenedioxythiophene (EDOT), propylene dioxythiophene (ProDOT), BTFTT , Pyrrole, anthracene, aniline, spiropyrane, substituted or unsubstituted acetylene and substituted or unsubstituted diacetylene, naphthopyran, phenantropyrane, dispulse red, dispers orange, fullgid, azobenzene and their It is characterized by a diarylethene copolymer prepared by polymerizing a compound having electrochemical activity such as a single compound selected from derivatives or a mixture of two or more thereof.

1) 0.01 to 95% by weight of a photochromic diaryl ethene compound represented by the formula (1); 2) 0.001 to 40% by weight of a metal oxidant containing a metal selected from alkali metals, Fe, Al, Zn, Mn, Cu and Ti; And 3) diaryl ethene polymer composition comprising 4 to 99.98% by weight of solvent.

1) 0.001 to 10 M of photochromic diaryl ethene compounds represented by the following general formula (1); 2) 0.001 to 10 M of electrolyte salt; And 3) a diaryl ethene polymer composition comprising 1 M of solvent.

In addition, the present invention is characterized by a nanostructure in which the diaryl ethene polymer composition is contained on a metal surface.

The diarylethene polymer composition containing the photochromic diarylethene compound capable of oxidative polymerization prepared according to the present invention and the nanostructure containing the composition are composed of a high concentration of photochromic compound to photochromic effect up to nanometer level. Not only can it lead to a uniform sensitivity, but also improves workability compared to the existing deposition methods, has excellent light transmittance, and can control the optical signal reversibly. There is an effect that can be widely used as a transmission medium.

The present invention is a photochromic diaryl ethene compound represented by Formula 1 specifically

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및

등을 사용할 수 있다. 그러나 본 발명은 상기 화합물에 한정되는 것은 아니다.

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And

Etc. can be used. However, the present invention is not limited to the compound.

The diaryl ethene compound has an oxidation level of 1.8 V or less (based on Ag / AgCl), preferably 0.2 to 1.8 V. If the oxidation level is less than 0.2 V, there is no storage stability and oxidation exceeds 1.8 V. A problem that is difficult to occur occurs.

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등을 사용할 수 있다. 그러나 본 발명은 이에 한정되는 것은 아니다.Reactants for preparing the diaryl ethene compound represented by the formula (1)

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And

Etc. can be used. However, the present invention is not limited thereto.

Preparation of the reactants is known in the art, Chem. Eur. J. 2001, 7 3466; Adv. Funct. Mater. 2003, 13 726; M acromolecules , 2006, 39 2823; 4. Org. Lett. , 2002, 4 607; Org. Lett., 2005. 7 3315; Bull. Chem. Soc. Jpn. , 1990, 63, 1311; J. Phys. Chem. C., 2007, 111 2770; Chem. Commun., 2002, 22, 2690; Macromolecules, 2006 39, 7844; Chemical Physics Letters, 2000, 328 234; Chemical Physics Letters, 2003, 373, 338; Adv. Mater., 2005 17 309; Adv. Mater., 1999, 11 1379; J. Mater. Chem. 2004, 14 1679; J. Photochem. Photobio A 2006, 178 162] and then polymerized it.

The polymerization is generally used in the art, but the present invention is not particularly limited, but the present invention may perform chemical polymerization using an oxidizing agent and electrochemical polymerization using a voltage corresponding to an oxidation level. There is a difference.

At this time, when chemical polymerization is carried out 1) 0.01 to 95% by weight of a photochromic diaryl ethene compound represented by the formula (1); 2) 0.001 to 40% by weight of a metal oxidant selected from alkali metals, Fe, Al, Zn, Mn, Cu and Ti; And 3) diaryl ethene polymer composition containing 4 to 99.98% by weight of a solvent.

If the diaryl ethene compound is less than 0.01% by weight, there is no photochromic property, and if it exceeds 95% by weight, it is difficult to control the thickness of the thin film. If the amount of the oxidizing agent is less than 0.001% by weight, polymerization does not occur and 40% by weight. When it exceeds%, it is preferable to maintain the above range because the low molecular weight causes a problem of poor thin film properties. In addition, when the amount of the solvent used is less than 4% by weight, the compound does not dissolve and polymerization does not occur. When the amount exceeds 99.98% by weight, the polymer does not grow, so it is preferable to maintain the above range.

The oxidant is a metal oxidant selected from alkali metals, Fe, Al, Zn, Mn, Cu and Ti, specifically, iron (III) chloride, iron (III) sulfate, iron (III) toluenesulfonate, aluminum (III) ) Chloride, titanium (IV) chloride, aluminum (III) toluenesulfonate, manganese (II) chloride, zinc (II) sulfate, copper sulfate, peroxodisulfate of alkali metal, ammonium peroxodisulfate, alkali metal A metal oxidant selected from among percarbonate, manganese dioxide and manganese (II) salts may be used. Since the oxidizing agent is used in the range of 0.001 to 40% by weight, if the amount of the oxidizing agent is less than 0.001% by weight, it will not be polymerized and if the amount exceeds 40% by weight, the thin film will not be formed.

It is also possible to mix phase transfer catalysts, which specifically include compounds containing —CH ₂ — and —O— structural units, such as polyethers prepared from crown ethers or ethylene oxide, for example 12-crown-4 Or 18-crown-6, benzo- or dibenzo-18-crown-6 and the like can be used, and quaternary ammonium salts, in particular quaternary containing alkyl radicals or arylalkyl radicals having 4 to 20 carbon atoms Ammonium salts and corresponding phosphorus compounds such as butyl-, decyl-, lauryl- or benzyltrimethylammonium salts and the like can be used. This phase transfer catalyst is used in the range of 0.001 to 40% by weight.

The solvent is an anhydrous solvent or a solvent having a low moisture content, the water content is preferably 5% by weight or less, specifically 0.01 to 5% by weight of water. Specifically, the solvent may be alcohol, ketone, ether, ester, chlorinated hydrocarbon, aliphatic or alicyclic hydrocarbon, and the like. Specifically, methanol, ethanol, propanol, butanol, pentanol, and 6 to 20 carbon atoms. Higher alcohols in the range, ethylene glycol, diethylene glycol, triethylene glycol or higher homologs in the range of 6 to 20 carbon atoms, acetone, butanone, methylene chloride, chloroform, tetrachloromethane, dichloroethane, trichloroethane, toluene, xylene, Chlorobenzene, dichlorobenzene, pentane, hexane, heptane, cyclohexane, octane, tetrahydrofuran, diethyl ether, methyl tert-butyl ether, ethylene glycol mono- or dimethyl ether, dimethylformamide, dimethylacetamide, N-methyl Pyrrolidone, ethyl or butyl acetate and the like can be used. The solvent is used in the range of 4 to 99.98% by weight. If the amount is less than 4% by weight, the polymerization does not occur and when the content exceeds 99.98% by weight, the molecular weight is low and a problem of poor thin film property is maintained. It is preferable.

In addition, when performing the CV method or the current method which is an electrochemical polymerization, 1) 0.001-10 M of photochromic diaryl ethene compounds represented by the said General formula (1); 2) 0.001 to 10 M of electrolyte salt, preferably 0.05 to 5 M; And 3) a diaryl ethene polymer composition containing 1 M of solvent.

When the amount of the diaryl ethene compound is less than 0.001 M, photochromism does not appear, and when the amount of the diaryl ethene compound exceeds 10 M, a problem of low photochromic contrast occurs. When the amount of the electrolyte salt is less than 0.001 M, no electrical polymerization occurs. If it exceeds 10 M, it is preferable to maintain the above range because a problem of eluting the compound from the solution occurs.

In this case, the electrolyte salt is generally used in the art, but is not particularly limited, and specifically, tetra-n-butylammonium perchlorate ( n -Bu ₄ NClO ₄ ), n -Bu ₄ NPF ₆ , n -Bu ₄ NBF ₄ , NaPF ₆ , NaBF ₄ , NaiClO ₄ , n -Et ₄ NClO ₄ , Liperchlorate (LiClO ₄ ), LiPF ₆ , LiBF ₄ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiCF ₃ SO ₃ , LiC (SO ₂ CF ₃ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₃ (C ₂ F ₅ ) ₃ , LiPF ₃ (CF ₃ ) ₃ , LiPF ₃ (iso-C ₃ F ₇ ) ₃ , a lithium salt containing a chain alkyl group such as LiPF ₅ (iso-C ₃ F ₇ ); _{(CF 2) 2 (SO 2} ) 2 may be used _{NLi, (CF 2) 3 (} SO 2) 2 lithium salt containing a cyclic alkylene chain such as NLi, such as sodium salts, ammonium salts. In particular, preferably _{n - Bu 4 NClO 4, n} -Bu 4 NPF 6, n -Bu 4 NBF 4, NaiClO 4, n -Et 4 NClO 4, lithium perchlorate _{(LiClO 4), LiN (SO} 2 CF 3) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiCF ₃ SO ₃ , LiC (SO ₂ CF ₃ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₃ (C ₂ F ₅ ) ₃ , LiPF ₃ (CF ₃ ) ₃ , LiPF ₃ (iso-C ₃ F ₇ ) ₃ , LiPF ₅ (iso-C ₃ F7). These electrolyte salts can use 1 type of single compound or 2 or more types of mixtures. The electrolyte salt is used in the range of 0.001 to 10 M. If the amount of the electrolyte salt is less than 0.001 M, electropolymerization does not occur and if the amount exceeds 10 M, the compound is eluted from the solution. Do.

The solvent is a non-aqueous solvent used in the art, specifically dichloromethane, crawlroform, acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, dimethylvinylene carbonate, vinyl ethylene Carbonate, methylethyl carbonate (MEC), methylpropyl carbonate, methylbutyl carbonate, ethylpropyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, dibutyl carbonate methyl propionate, methyl pivalate, Butyl pivalate, hexyl pivalate, octyl pivalate, dimethyl oxalate, ethyl methyl oxalate, diethyl oxalate, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-di Methoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, dimethylformamide, trimethyl phosphate, tributyl phosphate, Acid tri-octyl; Divinyl sulfone, γ-butyrolactone, δ-valerolactone, α-angelicalactone, adiponitrile, 1,4-propane sultone, 1,4-butanediol dimethane sulfonate, Propylene sulfite, glycol sulfate, propylene sulfate, dipropargyl sulfite, methyl propargyl sulfite, ethyl propargyl sulfite, 1,4-butanediol dimethane sulfonate, propylene sulfite, glyph Any one selected from lycol sulfate and propylene sulfate can be used.

Further, the present invention provides a photochromic compound or a compound having electrochemical activity, specifically ethylenedioxythiophene (EDOT), propylenedioxythiophene (ProDOT), BTFTT, pyrrole, anthracene, aniline, spiropyrane, substituted or unsubstituted acetylene A single compound or a mixture of two or more selected from the group and substituted or unsubstituted diacetylene, naphthopyran, phenanthropyran, dispulse red, disperse orange, fulgid, azobenzene and derivatives thereof can be used in combination. It may be contained in an amount of 0.001 to 700 parts by weight based on 100 parts by weight of the diaryl ethene polymer. The further compound may be copolymerized with a diarylethene derivative, or the diarylethene compound may be polymerized first or later, and the compound itself may be polymerized to form polymers and thin films of various structures. If the amount of the compound is less than 0.001 parts by weight, only the polymer polymerized from the compound of Formula 1 is expressed, and if it exceeds 700 parts by weight, photochromic properties are weak, so it is preferable to maintain the above range.

In addition, the polymer composition generally used in the art may contain a polymerization catalyst, an initiator, an antioxidant, a coloring agent, etc. for promoting the polymerization reaction, and such additives may be used by those skilled in the art. have.

When the electrochemical method is used, the voltage range uses a voltage before the decomposition occurs from the voltage at which oxidation occurs, specifically circulating or walking a voltage in the range of -3 V to 3 V. The current method is 0.01 microamps to 100 amps. When a current in the range is applied, the polymerization is caused by an oxidation reaction.

The present invention is characterized by a nanostructure consisting of the above-described diarylethene polymer composition on a metal surface, wherein the nanostructures are thin films, particles, rods, wires, and blocks. Various shape induction, such as, is possible. In this case, the thin film is coated on a metal substrate selected from ITO film, ITO glass, aluminum and copper.

Specifically, the diarylethene polymer composition of the present invention may be applied to various substrates such as plastic lenses, switches, filters, and windows to form a photoelectric characteristic film. The photoelectric characteristic film turns red when irradiated with ultraviolet rays and is visible. When the light is irradiated, it is changed to colorless, and can be repeatedly controlled by an ultraviolet / visible light source, and can be applied to sunscreen glasses, automobile windows, UV sensors, etc., which are colored when exposed to sunlight.

In particular, when the photoelectric characteristic film is applied to a plastic lens, it can be prepared by adding a composition comprising the formula (1) to the transparent plastic lens composition, wherein a conventional lens composition coating method can be used. In this case, there is an advantage that the lens can be applied to lenses having a different refractive index and various shapes.

In addition, the photoelectric characteristic film exhibits electrochromic properties, and may be used as an electrochromic device in which color is changed by voltage. In addition, an organic semiconductor, an optical recording medium, a display device, a recording device, an anti-counterfeiting film and a coating, a color changeable fiber, a color changeable container, or a medicine to which the diaryl ethene compound, the diaryl ethene polymer composition, etc. according to the present invention are applied It can be applied as a product of various uses.

Hereinafter, the present invention will be described in detail with reference to the following examples. The following examples are only for explaining the present invention in detail, and the scope of the present invention is not limited by these examples.

Example 1 Preparation of Compound 1

Well- known techniques [ Adv. Funct. Mater. 2003, 13 726] based on C ₁₄ H ₂₉ -EDOT-SnBu ₃ (1.2 g, 1.86 mmol) and known techniques [Ref. Chem. Eur. BTFI ₂ (0.64 g, 0.9 mmol) prepared from J. 2001, 7 3466] was dissolved in ultrapure toluene solution. Thereafter, PdCl ₂ (PPh ₃ ) ₂ (dichloro bis (trihenyl-phosphine) palladium (II), DTPP) was added to reflux. After 24 hours, the temperature was lowered to room temperature, the organic layer was separated with brine and NaHCO ₃ , the water was removed with MgSO ₄ , and the solvent was evaporated. After that, the residue was purified by chromatography to hexane and ethyl acetate (5: 1 weight ratio) to separate compound 1 with a purity of 99% or more (yield 57%).

¹ H NMR (300 MHz, CDCl ₃ ); δ 2.21 / 2.41 ppm (s, 6H), 0.96 ppm (s, -alkyl -CH _3, ), 1.33 ppm (m, -alkyl -CH ₂ ), 4.36 / 4.42 ppm (m, -OCH _2, 6H), 6.62 ppm (s, 2H), 7.62 ppm (ArH), 7.81 ppm (ArH), 8.13 ppm (ArH)

IR: 788, 1210, 1378, 1395, 1465, 1619, 1766, 2552, 3027

Mass: 1172.62

Oxidation Voltage (V, Ag / AgCl): 1.3 V

Photochromic: When the solution (10 ^-4 M) in which the compound 1 prepared in Example 1 was dissolved was irradiated with UV emitted from an ultraviolet spectrometer, the solution was blue violet, and the solution was visible light at 532 nm. Examining it returns to colorless again.

Example 2

After dissolving 0.93 g of BTFI ₂ in xylene (40 ml), 0.59 g of 3HTh-SnB synthesized from a known technique (Ref. Macromolecules , 2006, 39 2823) was dissolved in xylene and the catalyst PdCl ₂ (PPh ₃ ) ₂ (dichloro bis (trihenyl-phosphine) palladium (II), DTPP) was added to reflux. After 20 hours, the temperature was lowered to room temperature, the organic layer was separated with brine and NaHCO ₃ , the water was removed with MgSO ₄ , the solvent was evaporated, and then dissolved in toluene. SnBEDOT 0.56 g After dissolving in the solution, it was refluxed for 24 hours with the addition of PdCl ₂ (PPh ₃ ) ₂ catalyst. Subsequently, Compound 2 was separated using hexane and ethyl acetate by chromatography, and purified to 99% purity (yield 75%).

¹ H NMR (300 MHz, CDCl ₃ ); δ 2.18 / 2.32 ppm (s, 6H), 0.96 ppm (s, -alkyl-CH ₃ ), 1.29 ppm (m, -alkyl -CH ₂ ), 4.33 ppm (m, -OCH _2, 4H), 6.68 ppm ( s, H), 6.5 ppm (s, H) 7.63 ppm (ArH), 7.84 ppm (ArH), 8.22 ppm (ArH)

IR: 788, 1212, 1378, 1395, 1465, 1619, 1766, 2552, 3023

Mass: 774.92

Oxidation Voltage (V, Ag / AgCl): 1.2 V

Photochromic: When the solution 2 (10 ^-4 M) in which the compound 2 is dissolved is irradiated with UV emitted from the ultraviolet spectrometer, the solution becomes blue. When the solution is irradiated with visible light of 532 nm, the color returns to yellowish yellow.

Examples 3-20

In the same manner as in Example 1, except that Compounds 3 to 20 were prepared using the ingredients, solvents, and preparation methods shown in Table 1 below. At this time, each monomer used in the preparation of the compound was carried out using a known document as shown in Table 2.

The physical properties of the compounds 1 to 20 prepared above were measured by the following method, and the results are shown in Table 1 below.

[Measurement of physical properties]

(1) Thickness: Measured using Alpha-step IQ V2 (KLA Tencor).

(2) Photochromic: Color change is measured using an ultraviolet spectrometer.

(3) Oxidation voltage: measured by cyclic voltammetry method. The instrument is CHI624B (CH Instruments Inc), and the working electrode and counter electrode are platinum and the reference electrode is measured using Ag / AgCl.

(4) Photocurrent measurement of photoelectric film: The light source used was measured using UV (PowerArc UV100, 100 mW / cm ² ) and CHI624B (CH Instruments Inc) by chrono-coulometry method. . At this time, a solution of hydroquinone (5 mM) and potassium hydrogen phthalate (0.2 M) in a pH 4.0 buffer solution was prepared. The photoelectrode according to the present invention was used as a working electrode, and the counter electrode was made of platinum, As a reference electrode, silver / silver chloride (Ag / AgCl) was immersed in the buffer solution to calculate the current difference between when the working electrode was irradiated with UV light and when not.

(5) Number average molecular weight (Mn): After dissolving the sample in tetrahydrofuran (THF), it is measured on the basis of polystyrene using GPC of Younglin equipment.

Example Reactant (g) Product (Yield,%) Solvent (mL) Catalyst (g) Temperature (℃) / hour (hour) ¹ H NMR (300 MHz, CDCl ₃ ), δ Photochromic (color after UV irradiation) One C ₁₄ H ₂₉ -EDOT-SnB (1.2) BTFI ₂ (0.64) Compound 1 (57%) Toluene (70) DTPP (0.032) Reflux / 24 Example 1 2.21-2.41,0.96,1.33, 4.36-4.42,6.62,7.62, 7.81,8.13 Red 2 3-Hex-Th-SnB (0.59) BTFI ₂ (0.93) EDOT-SnB (0.56) Compound 2 (75%) Xylene (30) + Toluene (30), DTPP (0.016 +0.016) Reflux / 20 + 24 Example 2 2.18-2.32,0.96,1.29, 4.33,6.5,6.68,7.63, 7.84,8.22 Cheongbora 3 EDOST-SnB (0.58) PTFI ₂ (0.43) Compound 3 (70%) Toluene (40) + Xylene (20), DTPP (0.021) Reflux / 32 Example 1 2.22-2.32,3.61,6.65,3.72-4.32,7.63,7.81,8.20 blue 4 Me-EDOT-SnB (0.37) CNBTBr ₂ (0.26) Compound 4 (78%) Toluene (40) + Xylene (20), DTPP (0.032) Reflux / 24 Example 1 1.42,2.28-2.41,4.30-4.41,6.21,7.68,7.81,8.20 purple 5 EDOT-SnB (0.26) TFI ₂ (0.37) Compound 5 (68%) Toluene (40) + p-xylene (20), DTPP (0.002) RhCl (CO) (PPh ₃ ) ₂ (0.042) Reflux / 15 Example 1 2.28-2.41,4.36-4.48,6.23,6.68 6 MalBTI ₂ (0.40) EDNT-SnB (0.05) Compound 6 (78%) hexane (10) + toluene (20) Reflux / 32 Example 1 2.21-2.37,6.91,7.65,7.82,8.17,8.63 purple 7 MalThI ₂ (0.34) EDOT-SnB (0.56) Compound 7 (72%) Toluene (20) + p-xylene (20) RhCl (CO) (PPh ₃ ) ₂ (0.042) Reflux / 48 Example 1 2.20-2.28,4.35-4.46,6.72 Bluish violet 8 ProEDNT-SnB (0.6) CNTI ₂ (0.33) Compound 8 (78%) o-Xylene (5) + p-xylene (20), RhCl (CO) (PPh ₃ ) ₂ (0.042) + DTPP (0.02) Reflux / 12 Example 1 0.96,2.18-2.31,2.55,7.15,8.51-8.63 Brown 9 Me-TFI ₂ (0.38) EDOT-SnB (0.56) Compound 9 (81%) Hexane (10) + Toluene (70) DTPP (0.012) Reflux / 48 Example 1 2.27-2.40,2.51,4.32-4.42,6.57 blue 10 Me-FTFI ₂ (0.38) EDOT-SnB (0.25) EDNT-SnB (0.25) Compound 10 (75%) o-xylene (15) + p-xylene (20), DTPP (0.012) Reflux / 24 Example 1 1.81-2.20,0.18-2.31,4.36-4.43,6.35-6.87,8.63-8.72 Blue purple 11 EDOT-MEHB-SnB (0.86) BTFI ₂ (0.43) Compound 11 (82%) o-xylene (25) + p-xylene (20), DTPP (0.029) Reflux / 36 Example 1 0.96-1.25-1.29-1.33,2.28-2.41,3.52,4.25-4.32,6.35,7.05,7.65,7.82, 8.17 Fuchsia 12 HxOEDOT-SnB (1.5) BTFI2 (0.43) Compound 12 (70%) Hexane (10) + Toluene (20) + p-Xylene (20), DTPP (0.056) Reflux / 32 Example 1 0.96.1.29-1.33-1.6,2-2.55,4.36-4.42,6.37,7.63,7.81,8.20 Red 13 HxS-EDOT-SnB (0.82) BTFBr ₂ (0.43) Compound 13 (70%) p-xylene (20), DTPP (0.02) Reflux / 24 Example 1 0.93-1.23-1.66-2.52,4.31-4.42,6.41,7.63,7.79,8.05 maroon 14 HepO-EDOT-SnB (0.83) BTFI ₂ (0.43) Compound 14 (65%) Toluene (20), DTPP (0.022) Reflux / 38 Example 1 0.91-1.22-1.38-1.66-2.54,4.28-4.36,6.43,7.68,7.79,8.10 maroon 15 BTFI ₂ (0.43) 3-Hex-Th-SnB (0.59) Compound 15 (83%) Toluene (30) + p-xylene (20), DTPP (0.02) Reflux / 32 Example 1 0.96,1.29-1.33-1.62-2.52,2.18-2.41,6.72,6.85,7.51,7.86,8.10 Blue purple 16 BTFI ₂ (0.43) ProDOT-SnB (0.57) Compound 16 (83%) o-xylene (20) + p-xylene (20), DTPP (0.041) Reflux / 32 Example 1 2.17,2.21-2.38,3.74-3.94,7.51,7.86,8.10 purple 17 BTFI ₂ (0.43) Et-ProDOT-SnB (0.57) Compound 17 (83%) o-xylene (30) + p-xylene (20), DTPP (0.022) Reflux / 32 Example 1 0.96,1.29,2.23-2.39,2.49,3.76-3.94,7.61,7.86,8.11 purple 18 BTFI ₂ (0.43) ProDOT-SnB (0.59) C ₁₄ H ₂₉ -EDOT-SnB (0.38) Compound 18 (61%) Toluene (30 + 30), DTPP (0.027 + 0.032) Reflux / 32 + 24 Example 2 1.10,1.28,2.17,2.21-2.41,3.78-3.87,4.40-4.51,6.71-6.80,7.63,7.84,8.23 Red 19 BTFI ₂ (0.43) SnB-EG3-EDOT (0.73) Compound 19 (80%) Toluene (120), DTPP (0.042) Reflux / 72 Example 1 2.20-2.38,3.24-3.54-3.79-4.11,4.35-4.48,6.76,7.61,7.86,8.11 maroon 20 BTFHBr ₂ (0.5) PrDOT-SnB (1.5) Compound 20 (60%) o-xylene (20), RhCl (CO) (PPh ₃ ) ₂ (0.042) + DTPP (0.02) Reflux / 52 Example 1 0.96-1.29-1.33-1.62-2.55, 4.36-4.42, 6.37, 7.63, 7.81, 8.20 Red

Monomer constitutional formula references Monomer constitutional formula references BTFI ₂

Chem. Eur. J. 2001, 7 3466. TFI ₂

J. Phys. Chem. C. , 2007, 111 2770 SuBEDOT

Adv. Funct. Mater. 2003, 13 726   MEDOTSnB

Chem. Commun ., 2002, 22, 2690 3HexThSnB

M acromolecules , 2006, 39 2823   EDNTSnB

Macromolecules, 2006 39, 7844 EDOSTSnB

Org. Lett. , 2002, 4 607, MaBTI ₂

Chemical Physics Letters, 2000, 328 234 PTFI ₂

Org. Lett., 2005. 7. 3315, MalThMI ₂

Chemical Physics Letters, 2003, 373, 338 CNBTBr ₂

Bull. Chem. Soc. Jpn. , 1990, 63, 1311 DCNThMI ₂

Bull. Chem. Soc. Jpn. , 1990, 63, 1311

(continue)

Monomer constitutional formula references Monomer constitutional formula references PrEDNTSnB

Macromolecules, 2006 39, 7844 EtPrDOTSnB

Adv. Mater., 1999, 11 1379. MeThMI ₂ [12]

Adv. Mater., 2005 17 309 C ₁₄ H ₂₉ -EDOT-SnB

J. Mater. Chem. 2004, 14 1679. MeThSOI ₂

Bull. Chem. Soc. Jpn. , 1990, 63, 1311 BTFHI ₂

J. Photochem. Photobio A 2006, 178 162 PrDOTSnB

Adv. Mater., 1999, 11 1379. BTFHBr ₂

J. Photochem. Photobio A 2006, 178 162

or

=

The compounds prepared in Examples 1 to 20 are collectively shown in Table 3 below.

compound constitutional formula compound constitutional formula Compound 1

Compound 8

Compound 2

Compound 9

Compound 3

Compound 10

Compound 4

Compound 11

Compound 5

Compound 12

Compound 6

Compound 13

Compound 7

Compound 14

(continue)

compound constitutional formula compound constitutional formula Compound 15

Compound 18

Compound 16

Compound 19

Compound 17

Compound 20

Example 21 Polymerization with an Oxidizer

Compound 1 (0.5 g) prepared above was added to 30 mL of chloroform (CHCl ₃ ) in which FeCl ₃ (0.05 g) was dissolved, and stirred at room temperature for 12 hours to obtain a dark brown polymer. The polymer obtained above was precipitated by addition of methanol and dissolved in pure chloroform solution. An aqueous NH ₄ OH solution was added to the chloroform solution to wash and separate the organic layer. Then, methanol was added and precipitated to separate the polymer in a yield of 80%. The polymer prepared above had high solubility in organic solvents, and it was confirmed that the 6.35 ppm peak seen in NMR disappeared and polymerized to the thiophene position. GPC: number average molecular weight (Mn): 10800, (molecular weight distribution, Mn / Mw = 2.1)

0.5 g of the prepared polymer was dissolved in dichloromethane, coated on an ITO glass plate using a spin coater, and the solvent was dried. Thus, a photoelectrode coated with a purple thin film having a thickness of 100 nanometers was prepared. When the photoelectrode was immersed in a solution of hydroquinone (5 mM) and potassium hydrogen phthalate (0.2M) in a pH 4.0 buffer solution and irradiated with UV light, a photocurrent of 60 uA was generated.

Example 22

Compound 2 (0.5 g) and 1 g of BTFTT prepared above were added to 60 mL of chloroform (CHCl ₃ ) in which TiCl ₄ (0.12 g) was dissolved. After stirring for 10 hours at room temperature, the mixture was stirred for 5 hours while irradiating UV. Obtained. The polymer obtained above was precipitated by adding methanol. Drying after filtration produced a polymer having a yield of 70%.

GPC: number average molecular weight (Mn): 8021, (molecular weight distribution, Mn / Mw = 2.4)

Examples 23-25

The polymer was prepared by the same method as Example 21, but polymerized by a chemical method using a component, a solvent, an oxidizing agent, and the like shown in Table 4 below.

Example Monomer (g) Oxidizer (g), solvent (mL) Temperature (℃) / hour (hour) Polymer yield (%) Photocurrent Generation (uA) 21 Compound 1 (0.5) FeCl ₃ (0.05), CF (30) 25/12 (UV irradiation) 54 6 22 Compound 1 (0.5) + BTFTT (1) TiCl ₄ (0.12), CF (60) 25/10 + 5 (UV irradiation) 77 30 23 Compound 5 (0.58) + BTFTT (0.7) FeCl ₃ (0.1), CF (80) Example 22 25/24 + 2 (UV irradiation) 89 80 24 Compound 3 (0.8) + DR 1 (0.2) FeCl ₃ (0.1), MC (20) Example 21 40/15 54 21 25 Compound 4 (1.5) AlCl ₃ (0.1), MC (50) + AN (20) Example 22 40/15 + 2 (UV irradiation) 77 78 26 Compound 10 (0.65) FeCl ₃ (0.1), CH 2 Cl 2 (20) Example 22 20/5 + 2 (UV irradiation) 54 12 27 Compound 16 (0.58) FeCl ₃ (0.21) + iron (III) sulfate (0.1), AN (20) Example 21 40/72 87 60 28 Compound 17 (0.58) Na ₂ S ₂ O ₇ (0.1) + 18-crown-6 (0.1), CF (40) + ethanol (30) Example 21 40/28 71 0.8 29 Compound 1 (0.58) + EDOT (0.3) TiCl ₄ (0.1), CF (10) + MC (20) Example 22 40/5 + 2 (UV irradiation) 69 131 MC: dichloromethane, CF: chloroform, AN: acetonitrile, DR1: dispersed 1

Diaryl Ethylene Polymer Thin Film

Example 30 Thin Film Formation by Electropolymerization (CV Method)

Compound 16 (2 mM) prepared in Example 16 was added to dichloromethane in which 0.1 M of tetra-n-butylammonium perchlorate ( n- Bu ₄ NClO ₄ ) was dissolved. The working electrode was made of transparent ITO glass, the counter electrode was made of platinum wire, the reference electrode was made of Ag / AgCl, and the voltage was circulated in the range of -0.7 V to +1.5 V. After 10 voltage cycles, a purple polymer film with a thickness of 120 nm was formed on the ITO working electrode. The resulting polymer film was washed with an organic solvent and dried to prepare a photoelectric film in which a photoelectric polymer thin film was formed on ITO.

Example 31 Thin Film Formation by Electropolymerization (Current Method)

Compound 16 (2 mM) prepared in Example 16 was added to dichloromethane in which 0.1 M of tetra-n-butylammonium perchlorate ( n- Bu ₄ NClO ₄ ) was dissolved. The working electrode was made of a transparent ITO film, the counter electrode was made of stainless steel, the reference electrode was made of Ag / AgCl, and an electric current was applied for 5 minutes to produce a violet-purple polymer film having a thickness of 205 nm. The resulting polymer film was washed with an organic solvent and dried to produce a purified photoelectric polymer thin film.

Examples 32-40

The procedure was carried out in the same manner as in Example 31 or 32, except that the polymer was prepared electrochemically and a film was prepared as shown in Table 5 below.

Example Monomer (g) Electrolyte (M), Solvent (mL) Working electrode counter electrode Manufacturing method and condition Polymer thickness (nm) Photocurrent Generation (uA) 30 Compound 16 (0.2) n- Bu ₄ NClO ₄ (0.1 M), MC (10) ITO Glass Platinum Wire CV method (voltage range: -007 to +1.5 V, number of cycles: 10) 120 6 31 Compound 16 (0.3) n- Bu ₄ NClO ₄ (0.1 M), MC (10) ITO Glass Stainless Ammeter (current: 1 A, time: 5 minutes) 205 30 32 Compound 5 (0.58) + BTFTT (0.7) n- Bu ₄ NClO ₄ (0.2 M), MC (20) ITO Glass Platinum Wire CV method (voltage range: -1.0 to +1.8 V, number of cycles: 10) 135 80 33 Compound 3 (0.8) + DR 1 (0.2) n- Bu ₄ NClO ₄ (0.1 M), CF (50) ITO Glass Platinum Wire CV method (voltage range: 0 to +1.8 V, number of cycles: 7) 87 21 34 Compound 4 (1.5) n- Et ₄ NClO ₄ (0.1 M) + NaClO ₄ (0.05 M), AN (30) Aluminum plate platinum wire Ammeter (current: 1 A, time: 10 minutes) 240 78 35 Compound 10 (0.65) (CF ₂ ) ₃ (SO ₂ ) 2NLi (0.3 M) + NaClO ₄ (0.05 M), AN (10) + MC (40) Copper plate platinum wire CV method (voltage range: -1.5 to +1.7 V, number of cycles: 15) 320 122 36 Compound 16 (0.58) n -Et ₄ NClO ₄ (0.21M) + LiBF ₄ (0.05 M), EC (10) + PC (30) Stainless steel plate stainless steel plate Ammeter (current: 0.1 A, time: 30 minutes) 410 60 37 Compound 17 (0.58) LiClO ₄ (0.1M) + NaClO ₄ (0.05 M), AN (10) + PN (5) + MEC (5) ITO Glass Platinum Wire CV method (voltage range: -1.0 to +1.5 V, number of cycles: 20) 380 0.8 38 Compound 1 (0.58) + EDOT (0.3) n- Bu ₄ NClO ₄ (0.1 M), AN (50) + DMF (5) ITO Glass Platinum Wire CV method (voltage range: -1.0 to +1.7 V, cycles 15) 530 310 39 Compound 1 (0.05) + EDOT (0.3) + BTFTT (0.9) LiN (SO ₂ CF ₃ ) ₂ (0.2 M), MC (10) + CF (20) ITO Glass Platinum Wire CV method (voltage range: -1.0 to +1.7 V, number of cycles: 10) 315 340 40 Compound 17 (0.58) + BTFTT (0.5) LiCF ₃ SO ₃ (0.1 M), PC (10) + CF (20) ITO Glass Platinum Wire CV method (voltage range: -1.0 to +2.0 V, number of cycles: 50) 242 21 Comparative example BTFTT n- Bu ₄ NClO ₄ (0.2 M), MC (20) ITO Glass Platinum Wire CV method (voltage range: -1.0 to +1.8 V, number of cycles 10) 122 0.6 MC: dichloromethane, CF: chloroform, AN: acetonitrile, PN: propionitrile

1 shows a photograph of a polymer film coated on a transparent electrode in Example 39 according to the present invention.

Claims (13)

Photochromic diarylethene compounds represented by the following Chemical Formula 1: [Formula 1]

In Chemical Formula 1, R ¹ And R ² are the same or different, and CN, Cl, Br or R ¹ C═CR ² is

,

,

,

ego, Ar ¹ and Ar ² are the same or different,

or

to, In this case, R ³ and R ⁴ is an alkyl group having 1 to 20 carbon atoms or an alkyleneoxy group having 1 to 20 carbon atoms, and X ¹ and X ² are the same or different and each is -O-, -S- or -N (CH ₃ ). -Represents; The dashed line indicates the connecting portion towards the ethen as a connecting portion; Ar ³ and Ar ⁴ are the same or different

In this case, R ⁵ and R ⁶ is a benzene group, an alkyl group having 1 to 20 carbon atoms, an alkyl ester group having 1 to 20 carbon atoms, a polyalkyleneoxy having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, O- CH (R ⁷ ) CH ₂ O, O-CH ₂ CH (R ⁷ ) CH ₂ O, S-CH (R ⁸ ) CH ₂ S, S-CH (R ⁹ ) CH ₂ O or N = CH (R ¹⁰ ) CH = N substituents, these substituents are substituted in parts other than the linking portion (dotted line) of the aromatic ring; R ⁷ , R ⁸ , R <^9> and R <^10> is hydrogen, a C1-C20 alkyl, a C1-C20 alkylester group, a C1-C20 alkyleneoxy, or a C1-C20 alkoxy group, respectively. The method of claim 1, wherein the photochromic diaryl ethene compound

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

And

The compound characterized in that it is selected from. The compound of claim 1, wherein the diarylethene compound has an oxidation level of 1.8 V or less (based on Ag / AgCl). Diaryl ethene polymer, characterized in that the homopolymer prepared by polymerizing the photochromic diaryl ethene compound of any one of claims 1 to 3. Diaryl ethene polymer, characterized in that the copolymer prepared by polymerizing the photochromic diaryl ethene compound of any one of claims 1 to 3, and a compound having an electrochemical activity. The compound according to claim 5, wherein the compound having electrochemical activity is ethylenedioxythiophene (EDOT), propylenedioxythiophene (ProDOT), 3,4-ethylenedioxythiophene-substituted diarylethene (BTFTT), pyrrole , Anthracene, aniline, spiropyrane, substituted or unsubstituted acetylene and substituted or unsubstituted diacetylene, naphthopyran, phenantropyran, dispulse red, disperse orange, fullgid, azobenzene and derivatives thereof Polymer selected from a single compound or a mixture of two or more thereof. 6. The diarylethene polymer according to claim 4 or 5, wherein the polymerization is chemical polymerization or electropolymerization. 1) 0.01 to 95% by weight of a photochromic diarylethene compound represented by the following formula (1); 2) 0.001 to 40% by weight of a metal oxidant comprising a metal selected from alkali metals, Fe, Al, Zn, Mn, Cu and Ti; And 3) 4 to 99.98% by weight of solvent Diaryl ethene polymer composition, characterized in that consisting of: [Formula 1]

In Formula 1, R ¹ , R ² , Ar ¹ and Ar ² are the same as defined in Claim 1, respectively. 1) 0.001 to 10 M of photochromic diaryl ethene compound represented by the following formula (1); 2) 0.001 to 10 M of electrolyte salt; And 3) Solvent 1 M Diaryl ethene polymer composition, characterized in that consisting of: [Formula 1]

In Formula 1, R ¹ , R ² , Ar ¹ and Ar ² are the same as defined in Claim 1, respectively. 10. The ethylenedioxythiophene (EDOT), propylenedioxythiophene (ProDOT), 3,4-ethylenedioxythiophene-substituted diarylethene (BTFTT) based on 100 parts by weight of the diarylethene polymer. ), Pyrrole, anthracene, aniline, spiropyrane, substituted or unsubstituted acetylene and substituted or unsubstituted diacetylene, naphthopyran, phenanthropyran, dispulse red, dispers orange, fullgid, azobenzene and these Diaryl ethene polymer composition characterized in that it contains a single compound or a mixture of two or more selected from derivatives of 0.001 to 700 parts by weight. Nanostructure, characterized in that the metal surface, the diaryl ethene polymer composition of any one selected from claims 7 to 10 contained. The nanostructure of claim 11, wherein the nanostructure maintains a shape of a thin film, a particle, a rod, a wire, and a block. The nanostructure of claim 12, wherein the thin film is coated on a metal substrate selected from an ITO film, an ITO glass, aluminum, and copper.

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