Phenoxazine derivatives for the preparation of anodic materials for electrochromic devices, process for their preparation, anodic materials and electrochromic medium compositions

Abstract

The present application relates to the technical field of electrochromic materials, in particular to a phenoxazine derivative for preparing an anode material of an electrochromic device, a preparation method of the phenoxazine derivative, the anode material and an electrochromic medium composition. 17 are independently selected from H or unsubstituted C1-C7 alkoxy, and R7 is unsubstituted C1-C10 alkyl. The position of the oxidation state absorption peak is in the infrared waveband, which can be used to prepare near-infrared electrochromic devices.

Description

Technical Field

[0001] This invention relates to the field of electrochromic materials technology, and more specifically, to phenoxazine derivatives for preparing anode materials of electrochromic devices, their preparation methods, anode materials, and electrochromic media compositions. Background Technology

[0002] Electrochromism is a phenomenon in which the optical properties (reflectivity, transmittance, absorptivity, etc.) of a material undergo stable and reversible color changes under the influence of an applied electric field. In appearance, it manifests as reversible changes in color and transparency.

[0003] Based on the principle of electrochromic reactions, electrochromic materials can be divided into anodic and cathodic electrochromic materials. Currently, anodic electrochromic materials mainly consist of compounds such as ferrocene, triphenylamine, phenazine, and phenothiazine, as well as their derivatives. Their primary function is to modulate the visible light band. Solar radiation can be divided into ultraviolet, visible, and infrared bands, with energy proportions of 20%, 40%, and 40%, respectively. The aforementioned traditional electrochromic materials cannot effectively modulate infrared light, resulting in poor modulation capabilities. Therefore, developing electrochromic materials that can modulate the infrared band is of great significance to further promote the development of electrochromism.

[0004] In view of this, the present invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a phenoxazine derivative for preparing an anode material of an electrochromic device, a method for preparing the derivative, an anode material, and an electrochromic medium composition. An embodiment of this invention provides a novel compound whose oxidation-state absorption peak is located in the infrared band, and thus can be used to prepare a near-infrared electrochromic device.

[0006] This invention is implemented as follows:

[0007] In a first aspect, the present invention provides a phenoxazine derivative for preparing anode materials of electrochromic devices, wherein the derivative is selected from compounds shown in the structural formula:

[0008] Among them, R1-R6 and R8-R 17 Each is independently selected from H or unsubstituted C1-C7 alkoxy groups, and R7 is an unsubstituted C1-C10 alkyl group.

[0009] Secondly, the present invention provides an anode material for preparing an electrochromic device, the raw material of which includes the phenoxazine derivative described in any of the foregoing embodiments for preparing an anode material for an electrochromic device.

[0010] Thirdly, the present invention provides an electrochromic dielectric composition, the raw materials of which include a cathode material and the anode material for preparing electrochromic devices as described in the foregoing embodiments.

[0011] Fourthly, the present invention provides a method for preparing the phenoxazine derivative for preparing the anode material of an electrochromic device as described in the foregoing embodiments, wherein the synthesis is carried out according to the following synthetic route:

[0012]

[0013] Fifthly, the present invention provides an electrochromic device comprising the electrochromic medium composition described in the foregoing embodiments.

[0014] The present invention has the following beneficial effects: The embodiments of the present invention provide a new compound whose oxidation state absorption peak is located in the infrared band, and can be used to prepare near-infrared electrochromic devices, so that the electrochromic devices can achieve near-infrared modulation, which has great application potential in industries such as building windows, intelligent thermal control, filters and infrared military camouflage. Detailed Implementation

[0015] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0016] In a first aspect, the present invention provides a phenoxazine derivative for preparing anode materials of electrochromic devices, wherein the derivative is selected from compounds shown in the structural formula:

[0017] Among them, R1-R6 and R8-R 17 Each is independently selected from H or unsubstituted C1-C7 alkoxy groups.

[0018] Specifically, R1-R6 and R8-R 17 Each is independently selected from H or unsubstituted C1-C5 alkoxy groups; more preferably, it is any one of H, methoxy, and ethoxy groups. Furthermore, R 10 and R 15 For unsubstituted C1-C7 alkoxy groups, R1-R6, R8-R9, R 11 -R 14 and R 16 -R 17 It is hydrogen; R 10 and R 15 For unsubstituted C1-C5 alkoxy groups, R1-R6, R8-R9, R 11 -R14 and R 16 -R 17 It is hydrogen. For example, the alkoxy groups mentioned above, such as methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy.

[0019] R7 is an unsubstituted C1-C10 alkyl group; preferably an unsubstituted C1-C7 alkyl group; preferably an unsubstituted C1-C5 alkyl group, such as, but not limited to, any one of methyl, ethyl and propyl.

[0020] The phenoxazine derivative is selected from any one of the compounds shown in the following structural formulas:

[0021]

[0022] as well as

[0023] The phenoxazine derivatives used to prepare anode materials for electrochromic devices were synthesized according to the following synthetic route:

[0024]

[0025] For example:

[0026]

[0027] Specifically, in this invention, the anode material is prepared using phenoxazine derivatives as initial raw materials through a series of reactions such as alkylation, bromination, and CC coupling.

[0028] Thirdly, the present invention provides an anode material for preparing an electrochromic device, wherein the raw material comprises the phenoxazine derivative described in any of the foregoing embodiments for preparing an anode material for an electrochromic device.

[0029] The anode material may consist only of the aforementioned phenoxazine derivatives, or it may include other compounds.

[0030] Thirdly, the present invention provides an electrochromic dielectric composition, the raw materials of which include a cathode material and the anode material for preparing electrochromic devices as described in the foregoing embodiments.

[0031] The cathode material can be selected from octylviolet or other cathode materials in the prior art.

[0032] The molar ratio of the cathode material to the anode material is 1:(0.5-1.5). For example, it can be any value between 1:(0.5-1.5), such as 1:0.5, 1:1, 1:1.5, etc.

[0033] Furthermore, the concentrations of the cathode material and the anode material in the electrochromic medium composition are 1-100 mM, preferably 10-50 mM; specifically, the concentrations of the cathode material and the anode material can be selected according to the contrast requirements in the near-infrared range.

[0034] Fifthly, the present invention provides an electrochromic device comprising the electrochromic medium composition described in the foregoing embodiments.

[0035] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0036] Example 1

[0037] This invention provides a phenoxazine derivative with the following structural formula:

[0038]

[0039] The preparation method of this phenoxazine derivative is as follows:

[0040] Step 1: Phenyrazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol), and tetrahydrofuran were added to a three-necked flask, heated to 70 °C, and then iodomethane (6.81 g, 48 mmol) was added to initiate the reaction, which lasted for 12 h. After the reaction was complete, water was added to cool the mixture, followed by extraction with dichloromethane. The resulting organic phase was then rotary evaporated. After drying, petroleum ether was added, and the mixture was filtered. The filtrate was collected and dried to obtain 10-methyl-10H-phenyrazine (6.46 g, 82% yield).

[0041] Step 2: 10-methyl-10H-phenoxazine (6.46 g, 32.75 mmol) and tetrahydrofuran were added to a three-necked flask and cooled to 0 °C. Then, N-bromosuccinimide (11.66 g, 65.50 mmol) was added in small amounts several times. The reaction was stopped when the system color became lighter. Then, a small amount of sodium dithionite was added to quench the reaction. The mixture was then extracted with water and dichloromethane. The resulting organic phase was rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, 80% yield).

[0042] Step 3: 3,7-Dibromo-10-methyl-10H-phenoxazine (5.40 g, 15.20 mmol), p-methoxyphenylboronic acid (4.77 g, 31.44 mmol), potassium carbonate (4.34 g, 31.44 mmol), and dioxane were added to a three-necked flask, and the mixture was bubbled under nitrogen for 20 min. Then, tetra(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the mixture was heated to 110 °C and reacted for 16 h. After the reaction was complete, the mixture was extracted with water and dichloromethane. The resulting organic phase was rotary evaporated, dried, and then separated using a silica gel column (petroleum ether:dichloromethane = 4:1) to obtain the final product 3,7-bis(4-methoxyphenyl)-10-methyl-10H-phenoxazine (3.42 g, yield 55%).

[0043] The NMR data for this 3,7-bis(4-methoxyphenyl)-10-methyl-10H-phenoxazine are as follows:

[0044] 1 H NMR (C6D6, 500MHz) δ7.57 (m, J=2.2Hz, 4H, Ar-H), 7.36 (dd, J=4.1Hz, 2H, Ar-H), 7.24 (d, J=7.4Hz, 2H, Ar-H), 7.1 0 (m, J=8.6Hz, 2H, Ar-H), 6.78 (s, J=7.3Hz, 4H, Ar-H), 3.32 (m, J=7.1Hz, 6H, -CH3), 2.72 (s, J=6.7Hz, 3H, -CH3).

[0045] Example 2

[0046] This invention provides a phenoxazine derivative with the following structural formula:

[0047]

[0048] The preparation method of this phenoxazine derivative is as follows:

[0049] Step 1: Phenyrazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol), and tetrahydrofuran were added to a three-necked flask, heated to 70 °C, and then iodoethane (7.48 g, 48 mmol) was added to initiate the reaction, which lasted for 12 h. After the reaction was complete, water was added to cool the mixture, followed by extraction with dichloromethane. The resulting organic phase was then rotary evaporated. After drying, petroleum ether was added, and the mixture was filtered. The filtrate was collected and dried to obtain 10-ethyl-10H-phenyrazine (67.01 g, 83% yield).

[0050] Step 2: 10-Ethyl-10H-phenoxazine (6.46 g, 30.6 mmol) and tetrahydrofuran were added to a three-necked flask and cooled to 0 °C. Then, N-bromosuccinimide (11.66 g, 66.4 mmol) was added in small amounts several times. The reaction was stopped when the system color became lighter. A small amount of sodium dithionite was added to quench the reaction. The mixture was then extracted with water and dichloromethane. The resulting organic phase was rotary evaporated and dried to obtain the product 3,7-dibromo-10-ethyl-10H-phenoxazine (9.03 g, 80% yield).

[0051] Step 3: 3,7-Dibromo-10-ethyl-10H-phenoxazine (9.55 g, 25.88 mmol), p-methoxyphenylboronic acid (4.77 g, 31.44 mmol), potassium carbonate (4.34 g, 31.44 mmol), and dioxane were added to a three-necked flask, and the mixture was bubbled under nitrogen for 20 min. Then, tetra(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the mixture was heated to 110 °C and reacted for 16 h. After the reaction was complete, the mixture was extracted with water and dichloromethane. The resulting organic phase was rotary evaporated, dried, and then separated using a silica gel column (petroleum ether:dichloromethane = 4:1) to obtain the final product 3,7-bis(4-methoxyphenyl)-10-ethyl-10H-phenoxazine (6.3 g, yield 58%).

[0052] The NMR data for this 3,7-bis(4-methoxyphenyl)-10-ethyl-10H-phenoxazine are as follows:

[0053] 1 H NMR (C6D6, 500MHz) δ7.56 (m, J=6.2Hz, 4H, Ar-H), 7.35 (dd, J=4.1Hz, 2H, Ar-H), 7.23 (d, J=7.4Hz, 2H, Ar-H), 7.12 (m, J=8.6Hz, 2H, Ar-H), 6.77 (s, J=7.3Hz, 4H, Ar-H), 3.30 (s, J=7.2Hz, 6H, -CH3), 2.32 (d, J=6.2Hz, 2H, -CH2), 1.38 (m, J=6.7Hz, 3H, -CH3).

[0054] Example 3

[0055] This invention provides a phenoxazine derivative with the following structural formula:

[0056]

[0057] The preparation method of this phenoxazine derivative is as follows:

[0058] Step 1: Phenyrazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol), and tetrahydrofuran were added to a three-necked flask, heated to 70 °C, and then iodomethane (6.81 g, 48 mmol) was added to initiate the reaction, which lasted for 12 h. After the reaction was complete, water was added to cool the mixture, followed by extraction with dichloromethane. The resulting organic phase was then rotary evaporated. After drying, petroleum ether was added, and the mixture was filtered. The filtrate was collected and dried to obtain 10-methyl-10H-phenyrazine (6.46 g, 82% yield).

[0059] Step 2: 10-methyl-10H-phenoxazine (6.46 g, 35.30 mmol) and tetrahydrofuran were added to a three-necked flask and cooled to 0 °C. Then, N-bromosuccinimide (11.66 g, 65.50 mmol) was added in small amounts several times. The reaction was stopped when the system color became lighter. Then, a small amount of sodium dithionite was added to quench the reaction. The mixture was then extracted with water and dichloromethane. The resulting organic phase was rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, 80% yield).

[0060] Step 3: 3,7-Dibromo-10-methyl-10H-phenoxazine (6.46 g, 18.20 mmol), p-ethoxyphenylboronic acid (5.21 g, 31.44 mmol), potassium carbonate (4.34 g, 31.44 mmol), and dioxane were added to a three-necked flask, and the mixture was bubbled under nitrogen for 20 min. Then, tetra(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the mixture was heated to 110 °C and reacted for 16 h. After the reaction was complete, the mixture was extracted with water and dichloromethane. The resulting organic phase was rotary evaporated, dried, and then separated using a silica gel column (petroleum ether:dichloromethane = 4:1) to obtain the final product 3,7-bis(4-ethoxyphenyl)-10-methyl-10H-phenoxazine (3.82 g, yield 48%).

[0061] The NMR data for the above-mentioned 3,7-bis(4-ethoxyphenyl)-10-methyl-10H-phenoxazine are as follows:

[0062] 1 H NMR (C6D6, 500MHz) δ7.57 (m, J=7.2Hz, 4H, Ar-H), 7.34 (dd, J=6.8Hz, 2H, Ar-H), 7.25 (d, J=7.4Hz, 2H, Ar-H), 7.10 (m, J=8.6Hz, 2H, Ar-H), 6.79 (s, J=7.1Hz, 4H, Ar-H), 4.32 (d, J=6.2Hz, 4H, -CH2), 3.31 (m, J=7.3Hz, 3H, -CH3), 1.74 (s, J=6.9Hz, 6H, -CH3).

[0063] Example 4

[0064] This invention provides a phenoxazine derivative with the following structural formula:

[0065]

[0066] The preparation method of this phenoxazine derivative is as follows:

[0067] Step 1: Phenyrazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol), and tetrahydrofuran were added to a three-necked flask, heated to 70 °C, and then iodoethane (7.48 g, 48 mmol) was added to initiate the reaction, which lasted for 12 h. After the reaction was complete, water was added to cool the mixture, followed by extraction with dichloromethane. The resulting organic phase was then rotary evaporated. After drying, petroleum ether was added, and the mixture was filtered. The filtrate was collected and dried to obtain 10-ethyl-10H-phenyrazine (7.01 g, 83% yield).

[0068] Step 2: 10-Ethyl-10H-phenoxazine (6.46 g, 30.6 mmol) and tetrahydrofuran were added to a three-necked flask and cooled to 0 °C. Then, N-bromosuccinimide (11.66 g, 66.4 mmol) was added in small amounts several times. The reaction was stopped when the system color became lighter. A small amount of sodium dithionite was added to quench the reaction. The mixture was then extracted with water and dichloromethane. The resulting organic phase was rotary evaporated and dried to obtain the product 3,7-dibromo-10-ethyl-10H-phenoxazine (9.03 g, 80% yield).

[0069] Step 3: 3,7-Dibromo-10-ethyl-10H-phenoxazine (9.55 g, 25.88 mmol), p-ethoxyphenylboronic acid (5.21 g, 31.44 mmol), potassium carbonate (4.34 g, 31.44 mmol), and dioxane were added to a three-necked flask, and the mixture was bubbled under nitrogen for 20 min. Then, tetra(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the mixture was heated to 110 °C and reacted for 16 h. After the reaction was complete, the mixture was extracted with water and dichloromethane. The resulting organic phase was rotary evaporated, dried, and then separated using a silica gel column (petroleum ether:dichloromethane = 4:1) to obtain the final product 3,7-bis(4-ethoxyphenyl)-10-ethyl-10H-phenoxazine (6.07 g, yield 52%).

[0070] The NMR data for the above-mentioned 3,7-bis(4-ethoxyphenyl)-10-ethyl-10H-phenoxazine are as follows:

[0071] 1H NMR (C6D6, 500MHz) δ7.58 (m, J=6.7Hz, 4H, Ar-H), 7.33 (dd, J=7.5Hz, 2H, Ar-H), 7.23 (d, J=6.8Hz, 2H, Ar-H), 7.11 (m, J=7.3Hz, 2H, Ar-H), 6.7 7 (s, J=7.1Hz, 4H, Ar-H), 4.30 (d, J=7.5Hz, 4H, -CH2), 2.34 (d, J=6.8Hz, 2H, -CH2), 1.76 (s, J=7.2Hz, 6H, -CH3), 1.37 (m, J=7.3Hz, 3H, -CH3).

[0072] Comparative Example 1

[0073] This comparative example provides a phenoxazine derivative, the structural formula of which is shown below:

[0074]

[0075] Its preparation method is as follows:

[0076] Step 1: Phenyrazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol), and tetrahydrofuran were added to a three-necked flask, heated to 70 °C, and then iodomethane (6.81 g, 48 mmol) was added to initiate the reaction, which lasted for 12 h. After the reaction was complete, water was added to cool the mixture, followed by extraction with dichloromethane. The resulting organic phase was then rotary evaporated. After drying, petroleum ether was added, and the mixture was filtered. The filtrate was collected and dried to obtain 10-methyl-10H-phenyrazine (6.46 g, 82% yield).

[0077] Step 2: 10-methyl-10H-phenoxazine (6.46 g, 35.30 mmol) and tetrahydrofuran were added to a three-necked flask and cooled to 0 °C. Then, N-bromosuccinimide (11.66 g, 65.50 mmol) was added in small amounts several times. The reaction was stopped when the system color became lighter. Then, a small amount of sodium dithionite was added to quench the reaction. The mixture was then extracted with water and dichloromethane. The resulting organic phase was rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, 80% yield).

[0078] Step 3: 3,7-Dibromo-10-methyl-10H-phenoxazine (6.46 g, 18.20 mmol), p-ethoxyphenylboronic acid (3.06 g, 18.44 mmol), potassium carbonate (4.34 g, 31.44 mmol), and dioxane were added to a three-necked flask, and the mixture was bubbled under nitrogen for 20 min. Then, tetra(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the mixture was heated to 110 °C and reacted for 16 h. After the reaction was complete, the mixture was extracted with water and dichloromethane. The resulting organic phase was rotary evaporated, dried, and then separated using a silica gel column (petroleum ether:dichloromethane = 4:1) to obtain the final product 3-bromo-7-(4-ethoxyphenyl)-10-methyl-10H-phenoxazine (3.23 g, yield 48%).

[0079] The NMR data for the above-mentioned 3-bromo-7-(4-ethoxyphenyl)-10-methyl-10H-phenoxazine (3.23 g, yield 48%) are as follows:

[0080] 1 H NMR (DMSO-d6, 500MHz) δ7.61 (d, J=7.2Hz, 2H, Ar-H), 7.33-7.27 (m, 4H, Ar-H), 7.10-6.79 ( m, 4H, Ar-H), 4.05 (q, J=6.6Hz, 2H, -CH2), 3.20 (s, 3H, -CH3), 1.34 (t, J=6.2Hz, 3H, -CH3).

[0081] Comparative Example 2

[0082] This comparative example provides a phenoxazine derivative, the structural formula of which is shown below:

[0083]

[0084] The preparation method of this phenoxazine derivative is as follows:

[0085] Step 1: Phenyrazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol), and tetrahydrofuran were added to a three-necked flask, heated to 70 °C, and then iodomethane (6.81 g, 48 mmol) was added to initiate the reaction, which lasted for 12 h. After the reaction was complete, water was added to cool the mixture, followed by extraction with dichloromethane. The resulting organic phase was then rotary evaporated. After drying, petroleum ether was added, and the mixture was filtered. The filtrate was collected and dried to obtain 10-methyl-10H-phenyrazine (6.46 g, 82% yield).

[0086] Step 2: 10-methyl-10H-phenoxazine (6.46 g, 35.30 mmol) and tetrahydrofuran were added to a three-necked flask and cooled to 0 °C. Then, N-bromosuccinimide (11.66 g, 65.50 mmol) was added in small amounts several times. The reaction was stopped when the system color became lighter. Then, a small amount of sodium dithionite was added to quench the reaction. The mixture was then extracted with water and dichloromethane. The resulting organic phase was rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, 80% yield).

[0087] Step 3: 3,7-Dibromo-10-methyl-10H-phenoxazine (6.46 g, 18.20 mmol), o-ethoxyphenylboronic acid (3.06 g, 18.44 mmol), potassium carbonate (4.34 g, 31.44 mmol), and dioxane were added to a three-necked flask, and the mixture was bubbled under nitrogen for 20 min. Then, tetra(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the mixture was heated to 110 °C and reacted for 16 h. After the reaction was complete, the mixture was extracted with water and dichloromethane. The resulting organic phase was rotary evaporated, dried, and then separated using a silica gel column (petroleum ether:dichloromethane = 4:1) to obtain the final product 3-bromo-7-(4-ethoxyphenyl)-10-methyl-10H-phenoxazine (3.23 g, yield 48%).

[0088] The NMR data for the above-mentioned 3-bromo-7-(2-ethoxyphenyl)-10-methyl-10H-phenoxazine (3.23 g, yield 48%) are as follows:

[0089] 1 H NMR (DMSO-d6, 500MHz) δ7.99 (d, J=7.2Hz, 1H, Ar-H), 7.49-7.03 (m, 9H, Ar-H), 4.05 (q, J=6.6Hz, 2H, -CH2), 3.20 (s, 3H, -CH3), 1.55 (t, J=6.2Hz, 3H, -CH3).

[0090] Test Example 1

[0091] The potentials of the phenoxazine derivatives in Examples 1-4 and Comparative Examples 1-2 were measured using an electrochemical workstation. The potentials for Examples 1-4 were 0.66 V, 0.58 V, 0.52 V, and 0.49 V, respectively. The potentials for Comparative Examples 1 and 2 were 0.59 V and 0.57 V, respectively.

[0092] Test Example 2

[0093] The above-mentioned compound (anode material) was mixed with octyl viologen (cathode material) and dissolved in propylene carbonate to obtain an electrochromic medium. The concentrations of the cathode material and the anode material were 35 mmol and 45 mmol, respectively.

[0094] The electrochromic devices using the above four embodiments and two comparative examples as anode materials, with their properties and transmittance data at different wavelengths when applied with voltages from 1.0V to 2.0V, are shown in Table 1.

[0095] Table 1. Transmittance of electrochromic devices in neutral state and under applied voltages from 1.0V to 2.0V at different wavelengths.

[0096]

[0097] As shown in Table 1, the embodiments of the present invention, by introducing an alkyl group onto the N atom and an alkoxy group onto the benzene ring to donate electrons, reduce the redox potential. The longer the alkyl chain, the stronger the electron-donating ability, the more significant the potential reduction, and the lower the transmittance in the infrared band. Comparative Examples 1 and 2, compared to Examples 1-4, lack one conjugated benzene ring and show almost no response in the near-infrared band. This indicates that the phenoxazine derivatives provided in the embodiments of the present invention can achieve near-infrared modulation of electrochromic devices, and have great application potential in industries such as architectural windows, intelligent thermal control, filters, and infrared military camouflage.

[0098] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A phenoxazine derivative for preparing anode materials for electrochromic devices, characterized in that, It is selected from the compounds shown in the structural formula: Equation 1, where R 10 and R 15 For unsubstituted C1-C5 alkoxy groups, R1-R6, R8-R 9、 R 11 -R 14 and R 16 -R 17 R7 is hydrogen; R7 is an unsubstituted C1-C5 alkyl group.

2. The phenoxazine derivative for preparing an anode material for electrochromic devices according to claim 1, characterized in that, R7 is any one of methyl, ethyl, and propyl.

3. The phenoxazine derivative for preparing an anode material for electrochromic devices according to claim 1, characterized in that, The phenoxazine derivative is selected from any one of the compounds shown in the following structural formulas: , , as well as .

4. An anode material for preparing electrochromic devices, characterized in that, The raw materials include the phenoxazine derivatives described in any one of claims 1-3 for preparing anode materials for electrochromic devices.

5. An electrochromic medium composition, characterized in that, Its raw materials include cathode materials and the anode materials for preparing electrochromic devices as described in claim 4.

6. The electrochromic medium composition according to claim 5, characterized in that, The concentrations of the cathode material and the anode material in the electrochromic medium composition are 1-100 mM, respectively.

7. The electrochromic medium composition according to claim 6, characterized in that, The concentrations of the cathode material and the anode material in the electrochromic medium composition are 10-50 mM, respectively.

8. The electrochromic medium composition according to claim 6 or 7, characterized in that, The molar ratio of the cathode material to the anode material is 1:(0.5-1.5).

9. A method for preparing a phenoxazine derivative for preparing an anode material of an electrochromic device as described in claim 1, characterized in that, Perform the synthesis according to the following synthesis path: 。 10. An electrochromic device, characterized in that, It includes the phenoxazine derivatives for preparing anode materials of electrochromic devices as described in claim 1.

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