Aromatic amine compound containing oxadiazole and preparation method and application thereof

Abstract

The present invention discloses an oxadiazole-containing aromatic amine electrochromic compound and a preparation method and use thereof, wherein the oxadiazole-containing aromatic amine electrochromic compound exhibits excellent thermal stability and excellent dual-color electrochromic effect. The oxadiazole-containing aromatic amine electrochromic compound provided by the present invention is applied to a two-electrode system electrochromic device, and under the condition of adjusting different input voltages, an efficient, reversible, high-contrast chromaticity electrochromic effect can be achieved, which has broad application prospects in the fields of electrochromic glass, display, etc.

Description

Technical Field

[0001] The invention belongs to the field of organic functional materials and relates to an aromatic amine compound containing oxadiazole and a preparation method and application thereof. Background Art

[0002] Electrochromic materials are a type of functional materials whose color and transparency change significantly under the action of an electric field. They have been widely used in many fields such as low-energy display, goggles, anti-glare rearview mirrors, smart energy-saving glass and military camouflage. Electrochromic materials are generally divided into inorganic color-changing materials and organic color-changing materials. Typical representatives include tungsten trioxide, viologens and their derivatives, polythiophene organic polymers, and metal phthalocyanine compounds. To date, the research and development of electrochromic materials still has many challenging problems to be solved, such as the lack of rich color change types and the lack of obvious color contrast. Therefore, it is of great significance to research and develop electrochromic materials with multiple color changes and obvious chromaticity contrast.

[0003] As a class of functional groups with excellent electron transport properties, 1,3,4-oxadiazole and its derivatives can be used as electron acceptors (A) combined with strong electron donors (D, such as triarylamine, carbazole, etc.) to construct compounds with push-pull electron systems such as DA type or DAD type, which have excellent luminescence properties and can be used as fluorescent agents, scintillators or photosensitizers in electroluminescent devices, organic fluorescent sensors, etc. However, there are few studies on the research and development of oxadiazole and its derivatives in the field of electrochromism. Summary of the invention

[0004] In order to improve the above technical problems, the present invention provides an oxadiazole-containing aromatic amine electrochromic compound and a preparation method and application thereof. The aromatic amine organic compound of the present invention has excellent electrochromic properties.

[0005] The present invention provides an oxadiazole-containing aromatic amine compound represented by formula (I):

[0006]

[0007] in,

[0008] Each R is the same or different and is independently selected from one, two or more R a Substituted C 1-40 Alkyl, optionally substituted by one, two or more R a Substituted C 1-40 Alkoxy, optionally with one, two or more R b Substituted C 6-40 Aryl, optionally substituted by one, two or more R b Substituted C 5-40 heteroaryl;

[0009] R a is selected from H, halogen, amino, nitro, cyano, sulfonyl;

[0010] R b Selected from C 1-20 Alkyl, C 1-20 Alkoxy, C 1-20 Alkylthio, C 1-20 Silane, halogen, amino, nitro, cyano, sulfonyl.

[0011] In some embodiments, each R is the same or different and is independently selected from the group consisting of one, two or more R a Substituted C 1-20 Alkyl, optionally substituted by one, two or more R a Substituted C 1-20 Alkoxy, optionally with one, two or more R b Substituted C 6-20 Aryl, optionally substituted by one, two or more R b Substituted C 5-20 Heteroaryl.

[0012] In some embodiments, each R is the same or different and is independently selected from the group consisting of one, two or more R a Substituted C 1-10 Alkyl, optionally substituted by one, two or more R a Substituted C 1-10 Alkoxy, optionally with one, two or more R b Substituted C 6-10 Aryl, optionally substituted by one, two or more R b Substituted C 5-10 Heteroaryl.

[0013] In some embodiments, each R is the same or different and is independently selected from the group consisting of one, two or more R a Substituted C 1-10 Alkyl, optionally substituted by one, two or more R b Substituted C 6-10 Aryl.

[0014] In some embodiments, two R are the same and are selected from a Substituted C 1-10 Alkyl, optionally with one R b Substituted C 6-10 Aryl.

[0015] In some embodiments, R a Selected from H, halogen.

[0016] In some embodiments, R b Selected from C 1-10 Alkyl, C 1-10 Alkoxy, halogen.

[0017] In some embodiments, R b Selected from methyl, methoxy, halogen.

[0018] In some embodiments, both R are the same and are selected from methyl, phenyl, and methoxy-substituted phenyl.

[0019] In some embodiments, the oxadiazole-containing aromatic amine compound represented by formula (I) is selected from the following compounds:

[0020]

[0021] The present invention also provides a method for preparing the oxadiazole-containing aromatic amine compound represented by the above formula (I), the preparation method comprising the following steps:

[0022] (1) reacting p-iodobenzoylhydrazide with an aminobenzaldehyde derivative represented by formula M1 to obtain an intermediate represented by formula M2;

[0023] (2) reacting the intermediate represented by formula M2 with 3,6-di-tert-butylcarbazole to obtain an oxadiazole-containing aromatic amine compound represented by formula (I);

[0024]

[0025] wherein R is as defined above in the compound of formula (I).

[0026] In some embodiments, in step (1),

[0027] p-iodobenzoyl hydrazide reacts with an aminobenzaldehyde derivative represented by formula M1 in solvent-1, and solvent-1 is preferably ethanol, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, such as ethanol;

[0028] and / or, the reaction temperature is 60°C-100°C, for example 90°C;

[0029] And / or, the reaction time is 6 h to 20 h, such as overnight.

[0030] In some embodiments, step (1) further comprises the following steps:

[0031] After the reaction of p-iodobenzoylhydrazide and the aminobenzaldehyde derivative represented by formula M1 is completed, the reaction solution is poured into water, stirred and allowed to stand to obtain a solid precipitate; then, solvent-2 and sodium hypochlorite are added to the solid precipitate to continue the reaction. After the reaction is completed, the reaction solution is poured into water, extracted with solvent-3, and dried to obtain the intermediate represented by formula M2.

[0032] In some embodiments, solvent-2 and solvent-3 are the same or different and are independently selected from acetonitrile, dichloromethane, ethanol, and N,N-dimethylformamide.

[0033] In some embodiments, solvent-2 is acetonitrile and solvent-3 is dichloromethane.

[0034] In some embodiments, in step (2),

[0035] The intermediate represented by formula M2 reacts with 3,6-di-tert-butylcarbazole in the presence of a base, wherein the base is selected from potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, and potassium tert-butoxide;

[0036] and / or, the intermediate represented by formula M2 is reacted with 3,6-di-tert-butylcarbazole in the presence of a catalyst, wherein the catalyst is selected from cuprous iodide and 1,10-phenanthroline;

[0037] And / or, the intermediate represented by formula M2 is reacted with 3,6-di-tert-butylcarbazole in solvent-4, and solvent-4 is selected from N,N-dimethylformamide, xylene, N,N-dimethylacetamide, such as dry N,N-dimethylformamide.

[0038] In some embodiments, step (2) further comprises a post-processing step:

[0039] The reaction solution after the reaction of the intermediate represented by formula M2 and 3,6-di-tert-butylcarbazole is poured into water, extracted with solvent-5, dried, concentrated and purified to obtain an oxadiazole-containing aromatic amine compound represented by formula (I).

[0040] In some embodiments, solvent-5 is selected from dichloromethane, ethyl acetate.

[0041] In some embodiments, the preparation method comprises the following steps:

[0042] (1) 4-iodobenzoyl hydrazide and an aminobenzaldehyde derivative represented by formula M1 are heated to 90° C. in ethanol and reacted overnight; after the reaction is completed, the reaction solution is slowly poured into deionized water, stirred for 10 minutes and then allowed to stand for 2 hours; the solid precipitate is collected by filtration and vacuum dried, then placed in a single-mouth reaction flask, acetonitrile and sodium hypochlorite aqueous solution are added in sequence, and stirred at room temperature for half an hour; after the reaction is completed, the reaction solution is slowly poured into deionized water, extracted with dichloromethane, the organic phases are combined and dried over anhydrous sodium sulfate, and then concentrated under reduced pressure to obtain an intermediate represented by formula M2;

[0043] (2) Under a nitrogen atmosphere, the intermediate represented by formula M2 is added to 3,6-di-tert-butylcarbazole, potassium carbonate, cuprous iodide, 1,10-phenanthroline and dry N,N-dimethylformamide, and the mixture is heated under reflux to react overnight. The reaction solution is poured into water and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography to obtain an oxadiazole-containing aromatic amine compound represented by formula (I).

[0044] In some embodiments, purification of the obtained compound can be performed, for example, by purification using column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, sublimation purification, and the like.

[0045] In some embodiments, identification of the compounds can be performed by mass spectrometry, elemental analysis.

[0046] The present invention also provides the use of the oxadiazole-containing aromatic amine compound represented by the above formula (I) in the preparation of an electrochromic device.

[0047] The present invention also provides an electrochromic device, which contains the oxadiazole-containing aromatic amine compound represented by the above formula (I).

[0048] According to an embodiment of the present invention, the electrochromic device includes electrochromic smart dimming glass, an electrochromic display, an automobile automatic anti-glare rearview mirror, and electrochromic glasses.

[0049] According to the embodiment of the present invention, the structure of the electrochromic device can be various structures known in the prior art.

[0050] According to an embodiment of the present invention, the electrochromic device also includes conductive electrodes serving as an anode and a cathode, the anode and the cathode are arranged opposite to each other, and a cavity is formed by bonding the anode and the cathode around them with a colloid (such as butyl glue), and the cavity is filled with the oxadiazole-containing aromatic amine compound represented by the above formula (I).

[0051] According to an embodiment of the present invention, the anode and cathode are preferably transparent conductive glass, for example, ITO conductive glass or FTO conductive glass, preferably ITO conductive glass.

[0052] According to an embodiment of the present invention, the cavity is also filled with an electrolyte. Preferably, the electrolyte is at least one of tetra-n-butylammonium perchlorate, tetra-n-butylammonium hexafluorophosphate, potassium hexafluorophosphate and lithium hexafluorophosphate, preferably tetra-n-butylammonium perchlorate.

[0053] The present invention also provides a method for preparing an electrochromic device, comprising using transparent conductive glass as an anode and a cathode, and using a colloid (such as butyl glue) to surround a 2×2 cm 2The region is used to fill a mixed solution of an electrolyte and an oxadiazole-containing aromatic amine electrochromic compound represented by formula (I), and separate the anode and the cathode.

[0054] According to an embodiment of the present invention, the organic solvent used to prepare the mixed solution of electrolyte and electrochromic material is preferably nitrile, amide solvent or carbonate, more preferably N-methylpyrrolidone (NMP).

[0055] The present invention tests the performance of an electrochromic device assembled with the oxadiazole-containing aromatic amine compound represented by the above formula (I) as the electrochromic material:

[0056] When no voltage is applied, the electrochromic device appears nearly colorless or light yellow. When a voltage of 2.5 to 3.5 V is applied between the two electrodes of the device, the electrochromic compound containing oxadiazole and aromatic amines as shown in formula (I) exhibits dual coloration: an oxidation reaction may occur at the anode, and the electrochromic compound containing oxadiazole and aromatic amines as shown in formula (I) undergoes single-electron oxidation to be converted into positive monovalent cations, presenting a first coloring state; a reduction reaction may also occur on the cathode surface, and the electrochromic compound containing oxadiazole and aromatic amines as shown in formula (I) undergoes single-electron reduction to be converted into negative monovalent anions, presenting a second coloring state.

[0057] According to the different R substituents on the oxadiazole-containing aromatic amine electrochromic compound shown in formula (I), the first coloring state and the second coloring state can occur successively at different voltages, and the electrochromic device turns green or blue-green at a voltage of 2.5V, and turns dark brown at a voltage of 3.5V; the first coloring state and the second coloring state can also occur simultaneously at the same voltage, and the electrochromic device turns dark brown. When the external circuit is open and the voltage is stopped or the applied voltage is 0V, the electrochromic device is restored to the initial colorless or light yellow. The above color change process is cyclically reversible, and the device can be controlled to switch between the "transparent light color state" and the "dark color state" by adjusting the applied voltage.

[0058] Beneficial Effects

[0059] The present invention provides an oxadiazole-containing aromatic amine electrochromic compound represented by formula (I), which has good light and heat stability and excellent electrochromic performance, and has broad application prospects in the fields of electrochromic glass and the like. Specifically:

[0060] 1) The oxadiazole-containing aromatic amine organic compound of the present invention has excellent thermal stability, a decomposition temperature in air or nitrogen of greater than 350°C, and no glass transition occurs within a temperature range of room temperature to 200°C.

[0061] 2) The oxadiazole-containing aromatic amine organic compound of the present invention has obvious dual-color electrochromic properties in solution state, and can achieve reversible and controllable conversion between "transparent light-colored state" and "dark-colored state", so it has great application prospects in the field of color-changing glass.

[0062] Definition and explanation of terms

[0063] Unless otherwise specified, the definitions of groups and terms recorded in the specification and claims of this application, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, definitions of specific compounds in examples, etc., can be arbitrarily combined and combined with each other. The definitions of groups and compound structures after such combinations and combinations should be understood to be within the scope of the specification and / or claims of this application.

[0064] Unless otherwise specified, the numerical ranges recorded in this specification and claims are equivalent to recording at least each specific integer value therein. For example, the numerical range "1-40" is equivalent to recording each integer value in the numerical range "1-10", namely 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and each integer value in the numerical range "11-40", namely 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40. It should be understood that in the one, two or more used herein when describing substituents, "more" should refer to an integer ≥ 3, such as 3, 4, 5, 6, 7, 8, 9 or 10.

[0065] The term "halogen" or "halo" refers to fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

[0066] In general, the term "substituted" means that one or more hydrogen atoms in a given structure are replaced by a specific substituent. Further, when the group is substituted by more than one of the substituents, the substituents are independent of each other, that is, the more than one substituents may be different from each other or the same. Unless otherwise indicated, a substituent group may be substituted at each substitutable position of the substituted group. When more than one position in the given structural formula can be substituted by one or more substituents selected from a specific group, the substituents may be substituted at each position in the same or different manner. The substituents may be, but are not limited to, =O, hydrogen, deuterium, cyano, nitro, halogen, alkyl, haloalkyl, alkoxy, carboxyl, cycloalkyl, cycloalkyloxy, heterocyclyl, heterocyclylalkyl, aryl, arylalkyl, aryloxy, heteroaryl, heteroarylalkyl, heteroaryloxy, etc.

[0067] In addition, it should be noted that, unless otherwise explicitly stated, the description method "...independently selected" used in the present invention should be understood in a broad sense, meaning that the individuals described are independent of each other and can be independently selected from the same or different specific groups. In more detail, the description method "...independently selected" can mean that in different groups, the specific options expressed by the same symbols do not affect each other; it can also mean that in the same group, the specific options expressed by the same symbols do not affect each other.

[0068] In various parts of this specification, the substituents of the compounds disclosed in the present invention are disclosed according to group types or ranges. It is particularly pointed out that the present invention includes each independent subcombination of the individual members of these group types and ranges. For example, the term "C 1-6 "Alkyl" refers specifically to an independently disclosed C 1 Alkyl, C 2 Alkyl, C 3 Alkyl, C 4 Alkyl, C 5 Alkyl or C 6 alkyl.

[0069] In various parts of the present invention, linking substituents are described. When the structure clearly requires a linking group, the Markush variable listed for that group should be understood as a linking group. For example, if the structure requires a linking group and the Markush group definition for that variable lists "alkyl" or "aryl", it should be understood that the "alkyl" or "aryl" represents an alkylene group or an arylene group, respectively, that is linked.

[0070] The term "C 1-40 "Alkyl" means a straight or branched saturated monovalent hydrocarbon group having 1 to 40 carbon atoms. For example, "C 1-6 "Alkyl" means straight chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group may be optionally substituted with one or more substituents described herein. In some embodiments, the alkyl group contains 1-12 carbon atoms; in other embodiments, the alkyl group contains 1-6 carbon atoms; in yet other embodiments, the alkyl group contains 1-4 carbon atoms. Examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl butyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl or the like or isomers thereof.

[0071] The term "C 6-40 "Aryl" is understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 40 carbon atoms, preferably "C 6-14 The term "C 6-14 The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 Aryl), especially a ring having 6 carbon atoms ("C 6 aryl), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0072] The term "5-40 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems, including aromatic or partially aromatic ones, having 5 to 40 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include monovalent monocyclic, bicyclic or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, in each case may be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like. When the 5-20 membered heteroaryl is connected to other groups to form the compound of the present invention, the carbon atom on the 5-20 membered heteroaryl ring may be connected to other groups, or the heteroatom on the 5-20 membered heteroaryl ring may be connected to other groups. When the 5-20 membered heteroaryl is substituted, it may be monosubstituted or polysubstituted. In addition, there is no limitation on the substitution site, for example, the hydrogen connected to the carbon atom on the heteroaryl ring may be substituted, or the hydrogen connected to the heteroatom on the heteroaryl ring may be substituted.

[0073] Unless otherwise specified, heteroaryl includes all possible isomeric forms thereof, such as positional isomers thereof. Thus, for some illustrative non-limiting examples, it may include 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-positions, etc. (if present), one, two or more positions thereof, or forms bonded to other groups, including pyridin-2-yl, pyridin-2-ylene, pyridin-3-yl, pyridin-3-ylene, pyridin-4-ylene and pyridin-4-ylene; thienyl or thienylene includes thien-2-yl, thien-2-ylene, thien-3-ylene and thien-3-ylene; pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl.

[0074] The stereochemical definitions and conventions used herein generally follow SP Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York; and Eliel, E. and Wilen, S., "Stereochemistry of Organic Compounds", John Wiley & Sons, Inc., New York, 1994.

[0075] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0076] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Figure 1 This is the thermogravimetric curve of the oxadiazole-containing aromatic amine organic compound obtained in Example 1.

[0078] Figure 2 This is the thermogravimetric curve of the oxadiazole-containing aromatic amine organic compound obtained in Example 2.

[0079] Figure 3 This is the thermogravimetric curve of the oxadiazole-containing aromatic amine organic compound obtained in Example 3.

[0080] Figure 4 The DSC curve of the oxadiazole-containing aromatic amine organic compound prepared in Example 1 is shown in FIG.

[0081] Figure 5 This is the DSC curve of the oxadiazole-containing aromatic amine organic compound obtained in Example 2.

[0082] Figure 6The DSC curve of the oxadiazole-containing aromatic amine organic compound obtained in Example 3 is shown in FIG.

[0083] Figure 7 The absorption spectra of the electrochromic device prepared in Example 4 under different voltage conditions are shown.

[0084] Figure 8 The absorption spectra of the electrochromic device prepared in Example 5 under different voltage conditions are shown.

[0085] Fig. 9 The absorption spectra of the electrochromic device prepared in Example 6 under different voltage conditions are shown. DETAILED DESCRIPTION

[0086] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0087] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0088] Example 1: Preparation of 2-[4-(dimethylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (1)

[0089] Under nitrogen atmosphere, p-iodobenzoyl hydrazide (2.10 g, 8 mmol) and 4-(dimethylamino)-benzaldehyde (1.19 g, 8 mmol) were added to 80 mL of ethanol, and the reaction solution was heated to 90 ° C and stirred overnight. After cooling to room temperature, the reaction solution was slowly poured into 400 ml of deionized water, stirred for 10 min, and allowed to stand for 2 h. The light yellow solid was collected by filtration and vacuum dried at 80 ° C for 4 h. The dried intermediate was placed in a single-mouth reaction flask, and 80 ml of acetonitrile and 120 ml of sodium hypochlorite solution were added in sequence, and stirred at room temperature for 30 min. The reaction solution was slowly poured into 400 ml of deionized water and extracted with dichloromethane (200 mL × 3). The organic phases were combined and washed with deionized water. The obtained organic phase was purified by anhydrous NaSO 4 Drying and rotary evaporation concentration gave a light yellow intermediate M2-1.

[0090] Under nitrogen atmosphere, the above light yellow intermediate M2-1 (0.76 g, 1.9 mmol), 3,6-di-tert-butylcarbazole (0.71 g, 2.5 mmol), K 2 CO 3(0.71 g, 5 mmol), CuI (97.2 mg, 0.5 mmol) and 1,10-phenanthroline (91.2 mg, 0.5 mmol) were added to 10 ml of dry DMF in sequence, and the reaction solution was heated to 145 ° C and cooled after 8 h of reaction. After cooling to room temperature, solid impurities were filtered out, and then extracted with dichloromethane (200 mL x 3), and the organic phases were combined and washed with deionized water. The obtained organic phase was treated with anhydrous NaSO 4 The reaction mixture was dried and concentrated by rotary evaporation to obtain a yellow crude product, which was separated and purified by column chromatography (petroleum ether:ethyl acetate=5:1) to obtain a white solid product 2-[4-(dimethylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (1) (0.64 g, 1.1 mmol) with a yield of 60%.

[0091] The product was characterized by NMR and elemental analysis, confirming that the pure target product was obtained in this example:

[0092] NMR: 1 H NMR (400MHz, Chloroform-d) δ = 8.34 (d, J = 8.6Hz, 2H), 8.15 (s, 2H), 8.04 (d, J = 8.4Hz, 2H), 7 .75(d,J=8.5Hz,2H),7.52–7.43(m,4H),6.86(d,J=8.5Hz,2H),3.10(s,6H),1.48(s,18H). 13 C NMR (100 MHz, Chloroform-d) δ = 165.49, 163.21, 152.35, 143.60, 141.02, 138.75, 128.51, 128.35, 126.76, 123.96, 123.87, 122.52, 116.50, 111.96, 109.33, 40.38, 34.88, 32.08. Elemental analysis (C 36 H 38 N 4 O) Calculated: N, 10.32; C, 79.67; H, 7.06; Measured: N, 10.34; C, 79.85; H, 7.11.

[0093] The thermogravimetric curve of 2-[4-(dimethylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (1) is shown in Figure 1 As shown, the DSC curve is Figure 4 Analysis Figure 1 and Figure 4It can be seen that the compound has excellent thermal stability, a decomposition temperature of 350°C, and no glass transition occurs in the temperature range from room temperature to 200°C, which can meet the needs of production preparation processes and actual application scenarios.

[0094] Example 2: Preparation of 2-[4-(diphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (2)

[0095] Under nitrogen atmosphere, p-iodobenzoyl hydrazide (2.62 g, 10 mmol) and 4-diphenylaminobenzaldehyde (2.76 g, 10 mmol) were added to 100 mL of ethanol, and the reaction solution was heated to 90 ° C and stirred overnight. After cooling to room temperature, the reaction solution was slowly poured into 500 ml of deionized water, stirred for 10 min, and allowed to stand for 2 h. The bright yellow solid was collected by filtration and vacuum dried at 80 ° C for 4 h. The dried intermediate was placed in a single-mouth reaction flask, and 100 ml of acetonitrile and 150 ml of sodium hypochlorite solution were added in sequence, and stirred at room temperature for 30 min. The reaction solution was slowly poured into 500 ml of deionized water and extracted with dichloromethane (200 mL × 3). The organic phases were combined and washed with deionized water. The obtained organic phase was purified by anhydrous NaSO 4 The mixture was dried and concentrated by rotary evaporation to obtain the khaki intermediate M2-2.

[0096] Under nitrogen atmosphere, the above light yellow intermediate M2-2 (1.03 g, 2 mmol), 3,6-di-tert-butylcarbazole (0.70 g, 2.5 mmol), K 2 CO 3 (0.70 g, 5 mmol), CuI (97.9 mg, 0.5 mmol) and 1,10-phenanthroline (90.9 mg, 0.5 mmol) were added to 10 ml of dry DMF in sequence, and the reaction solution was heated to 145 ° C and cooled after 8 h of reaction. After cooling to room temperature, solid impurities were filtered out, and then extracted with dichloromethane (200 mL x 3), and the organic phases were combined and washed with deionized water. The obtained organic phase was treated with anhydrous NaSO 4 The reaction mixture was dried and concentrated by rotary evaporation to obtain a yellow crude product, which was separated and purified by column chromatography (petroleum ether:ethyl acetate=5:1) to obtain a white solid product 2-[4-(diphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (2) (0.83 g, 1.25 mmol) with a yield of 62.5%.

[0097] The product was characterized by NMR and elemental analysis, confirming that the pure target product was obtained in this example:

[0098] NMR: 1H NMR (400MHz, Chloroform-d) δ = 8.34 (d, J = 8.6Hz, 2H), 8.16 (s, 2H), 7.99 (d, J = 8.9Hz, 2H), 7. 77(d,J=8.6Hz,2H),7.53–7.44(m,4H),7.38–7.32(m,4H),7.22–7.12(m,8H),1.48(s,18H). 13 C NMR (100 MHz, Chloroform-d) δ = 164.87, 163.65, 151.17, 146.73, 143.67, 141.28, 138.71, 129.75, 128.46, 128.18, 126.78, 125.85, 124.57, 123.98, 123.92, 122.21, 121.17, 116.52, 115.99, 109.32, 34.88, 32.08. Elemental analysis (C 46 H 42 N 4 O) Calculated: N, 8.40; C, 82.85; H, 6.35; Measured: N, 8.40; C, 83.09; H, 6.38.

[0099] The thermogravimetric curve of 2-[4-(diphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (2) is shown in Figure 2 As shown, the DSC curve is Figure 5 Analysis Figure 2 and Figure 5 It can be seen that the compound has excellent thermal stability, a decomposition temperature of 400°C, and no glass transition occurs in the temperature range from room temperature to 200°C, which can meet the needs of production and preparation processes and actual application scenarios.

[0100] Example 3: Preparation of 2-[4-(4,4'-dimethoxydiphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (3)

[0101] Under nitrogen atmosphere, 4-(4,4'-dimethoxydiphenylamine)-benzaldehyde (2.50g, 7.5mmol) and p-iodobenzoylhydrazide (1.95g, 7.5mmol) were added to 60mL ethanol, and the reaction solution was heated to 90°C and stirred overnight. After cooling to room temperature, the reaction solution was slowly poured into 300ml deionized water, stirred for 10min, and allowed to stand for 2h. The yellow solid was collected by filtration and vacuum dried at 80°C for 4h. The dried intermediate was placed in a single-mouth reaction flask, and 60ml acetonitrile and 90ml sodium hypochlorite solution were added in sequence, and stirred at room temperature for 30min. The reaction solution was slowly poured into 300ml deionized water and extracted with dichloromethane (200mL×3). The organic phases were combined and washed with deionized water. The obtained organic phase was purified by anhydrous NaSO 4 Drying and rotary evaporation concentration gave a light yellow intermediate M2-3.

[0102] Under nitrogen atmosphere, the above light yellow intermediate M2-3 (0.70 g, 1.2 mmol), 3,6-di-tert-butylcarbazole (0.56 g, 2.0 mmol), K 2 CO 3 (0.55 g, 4 mmol), CuI (73.6 mg, 0.4 mmol) and 1,10-phenanthroline (80.2 mg, 0.4 mmol) were added to 10 ml of dry DMF in sequence, and the reaction solution was heated to 145 ° C and cooled after 8 h of reaction. After cooling to room temperature, solid impurities were filtered out, and then extracted with dichloromethane (200 mL x 3), and the organic phases were combined and washed with deionized water. The obtained organic phase was treated with anhydrous NaSO 4 The reaction mixture was dried and concentrated by rotary evaporation to obtain a yellow crude product, which was separated and purified by column chromatography (dichloromethane:ethyl acetate=10:1) to obtain a light yellow solid product 2-[4-(4,4'-dimethoxyphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazole-9-yl)phenyl]-1,3,4-oxadiazole (3) (0.48 g, 0.7 mmol) with a yield of 55%.

[0103] The product was characterized by NMR and elemental analysis, confirming that the pure target product was obtained in this example:

[0104] NMR: 1H NMR (400MHz, Chloroform-d) δ = 8.31 (d, J = 8.6Hz, 2H), 8.14 (s, 2H), 7.92 (d, J = 8.9Hz, 2H), 7.74 (d, J = 8.5Hz, 2H), 7.49 (d, J=8.7Hz,2H),7.43(d,J=8.7Hz,2H),7.16–7.12(m,4H),6.97–6.93(m,2H),6.91–6.87(m,4H),3.82(s,6H),1.46(s,18H). 13 CNMR (100MHz, Chloroform-d) δ=165.02,163.38,157.03,152.01,143.66,141.24,139.44,138.70,128.43,128.24,127.81,126.76,123.97,123.90,122.19,118.19,116.51,115.09,113.83,109.31,55.61,34.87,32.07. Elemental analysis (C 48 H 46 N 4 O 3 ) Calculated value: N, 7.71; C, 79.31; H, 6.38; Measured value: N, 7.23; C, 79.54; H, 6.78.

[0105] The thermogravimetric curve of 2-[4-(4,4'-dimethoxydiphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazol-9-yl)phenyl]-1,3,4-oxadiazole (3) is shown in Figure 3 As shown, the DSC curve is Figure 6 Analysis Figure 3 and Figure 6 It can be seen that the compound has excellent thermal stability, a decomposition temperature of 400°C, and no glass transition occurs in the temperature range from room temperature to 200°C, which can meet the needs of production and preparation processes and actual application scenarios.

[0106] Example 4: Assembly and testing of an electrochromic device based on the compound prepared in Example 1

[0107] The electrochromic properties of the oxadiazole-containing aromatic amine organic compound 2-[4-(dimethylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazole-9-yl)phenyl]-1,3,4-oxadiazole (1) prepared in Example 1 were investigated. A 2×2 cm 2The area is then covered with another piece of ITO conductive glass, and 0.5 ml of N-methylpyrrolidone solution dissolved with tetra-n-butylammonium perchlorate electrolyte (1M) and the aromatic amine organic compound 2-[4-(dimethylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazole-9-yl)phenyl]-1,3,4-oxadiazole (1) (25 mg / mL) prepared in Example 1 is injected into the gap area in the middle to obtain a two-electrode electrochromic device.

[0108] The performance test of the electrochromic device prepared above was carried out on Shanghai Chenhua CHI660D electrochemical instrument in constant potential mode in room temperature air environment. The absorption spectra at different voltages are shown in Figure 2. Figure 7 As shown. The black dotted line is the spectrum in the faded state. As the voltage applied between the two electrodes of the electrochromic device increases, the electrochromic solution has three absorption peaks at 435nm, 470nm and 540nm, reaching the maximum value when the applied voltage is 3.4V ( Figure 7 ), at which time the electrochromic device is in a brown coloring state. This coloring state can be restored to the initial transparent light-colored state when the applied voltage drops to 0V or the voltage is disconnected, thereby realizing a cyclic reversible process between the "transparent light-colored state" and the "brown coloring state".

[0109] Example 5: Assembly and testing of electrochromic devices based on the compounds prepared in Example 2

[0110] The electrochromic properties of the oxadiazole-containing aromatic amine organic compound 2-[4-(diphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazole-9-yl)phenyl]-1,3,4-oxadiazole (2) prepared in Example 2 were investigated. A 2×2 cm 2 The area is then covered with another piece of ITO conductive glass, and 0.5 ml of N-methylpyrrolidone solution dissolved with tetra-n-butylammonium perchlorate electrolyte (1M) and the aromatic amine organic compound 2-[4-(diphenylamino)-phenyl]-5-[4-(3,6-di-tert-butylcarbazole-9-yl)phenyl]-1,3,4-oxadiazole (2) (25 mg / mL) prepared in Example 2 is injected into the gap area in the middle to obtain a two-electrode electrochromic device.

[0111] The performance test of the electrochromic device prepared above was carried out on Shanghai Chenhua CHI660D electrochemical instrument in constant potential mode in room temperature air environment. The absorption spectra at different voltages are shown in Figure 2. Figure 8As shown. The black dashed line is the spectrum in the faded state. As the voltage applied between the two electrodes of the electrochromic device increases, two new strong absorption peaks appear at 485nm and 705nm in the electrochromic solution, reaching the maximum value when the applied voltage is 3.5V ( Figure 8 ), at which time the electrochromic device is in a dark brown coloring state. This coloring state can be restored to the initial transparent light coloring state when the applied voltage drops to 0V or the voltage is disconnected, thereby realizing a cyclic reversible process between the "transparent light coloring state" and the "dark brown coloring state".

[0112] Example 6: Assembly and testing of electrochromic devices based on the compounds prepared in Example 3

[0113] The electrochromic properties of the oxadiazole-containing aromatic amine organic compound 2-[4-(4,4'-dimethoxydiphenylamine)-phenyl]-5-[4-(3,6-di-tert-butylcarbazole-9-yl)phenyl]-1,3,4-oxadiazole (3) prepared in Example 3 were investigated. A 2×2 cm 2 The area is then covered with another piece of ITO conductive glass, and 0.5 ml of N-methylpyrrolidone solution dissolved with tetra-n-butylammonium perchlorate electrolyte (1M) and the aromatic amine organic compound 2-[4-(4,4'-dimethoxydiphenylamine)-phenyl]-5-[4-(3,6-di-tert-butylcarbazole-9-yl)phenyl]-1,3,4-oxadiazole (3) (25 mg / mL) prepared in Example 3 is injected into the gap area in the middle to obtain a two-electrode electrochromic device.

[0114] The performance test of the electrochromic device prepared above was carried out on Shanghai Chenhua CHI660D electrochemical instrument in constant potential mode in room temperature air environment. The absorption spectra at different voltages are shown in Figure 2. Fig. 9 As shown. The black dotted line is the spectrum in the faded state. As the voltage applied between the two electrodes of the electrochromic device increases, when the voltage is 2.5V, the electrochromic solution has a new strong absorption peak at 770nm. At this time, the electrochromic device is in a blue-green coloring state ( Fig. 9 As the voltage continues to increase, a new absorption peak appears at 490nm, reaching a maximum value when the applied voltage is 3.5V ( Fig. 9 ), at which time the electrochromic device is in a dark brown coloring state. When the applied voltage drops to 0V or the voltage is disconnected, the coloring state can be restored to the initial transparent light coloring state, thereby realizing a cyclic reversible process between the "transparent light coloring state" to the "blue-green coloring state" and the "dark brown coloring state" dual coloring states.

[0115] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. Application of an oxadiazole-containing aromatic amine compound represented by formula (I) in the preparation of an electrochromic device: In formula (I), two R are the same and are selected from C 1-4 Alkyl, phenyl, C 1-10 Alkoxy substituted phenyl.

2. The use according to claim 1, characterized in that: The oxadiazole-containing aromatic amine compound represented by formula (I) is selected from the following compounds:

3. An electrochromic device, comprising the oxadiazole-containing aromatic amine compound represented by formula (I) in the application according to any one of claims 1 to 2.

4. The electrochromic device according to claim 3, characterized in that: Electrochromic devices include electrochromic smart dimming glass, electrochromic displays, automotive automatic anti-glare rearview mirrors, and electrochromic glasses.

5. The electrochromic device according to claim 3 or 4, characterized in that: The electrochromic device also includes conductive electrodes as an anode and a cathode, the anode and the cathode are arranged opposite to each other, a cavity is formed around the anode and the cathode by colloid bonding, and the cavity is filled with an oxadiazole-containing aromatic amine compound represented by formula (I) in the application described in any one of claims 1-2.

6. A method for preparing an electrochromic device, comprising using transparent conductive glass as an anode and a cathode, and using a colloid to form a 2×2 cm 2 The region is used to fill the electrolyte and a mixed solution of the oxadiazole-containing aromatic amine compound represented by formula (I) in the application according to any one of claims 1 to 2, and separate the anode and the cathode.

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