Phenoxazine derivative for preparing anode material of electrochromic device, preparation method of phenoxazine derivative, anode material and electrochromic medium composition

Abstract

The invention 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. The phenoxazine derivative is a compound shown in the structural formula: # imgabs0 #, R1-R6 and R8-R17 are respectively and independently selected from H or unsubstituted C1-C7 alkoxy, and R7 is unsubstituted C1-C10 alkyl. The position of an oxidation-state absorption peak is in an infrared band, so that the material can be used for preparing a near-infrared electrochromic device.

Description

Technical Field

[0001] The present invention relates to the technical field of electrochromic materials, and in particular to phenoxazine derivatives for preparing anode materials of electrochromic devices, preparation methods thereof, anode materials and electrochromic medium compositions. Background Art

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

[0003] According to the principle of electrochromic reaction, electrochromic materials can be divided into anode electrochromic materials and cathode electrochromic materials. At present, anode electrochromic materials are mainly ferrocene, triphenylamine, phenazine, phenothiazine and other compounds and their derivatives. It is mainly regulated in the visible light band. The distribution of solar radiation bands can be divided into ultraviolet light band, visible light band and infrared light band, and their energy accounts for 20%, 40% and 40% respectively. The above-mentioned traditional electrochromic materials cannot effectively modulate the light in the infrared band, which makes the electrochromic materials have poor regulation ability. Therefore, in order to further promote the development of electrochromism, it is of great significance to develop electrochromic materials that can be used to regulate the infrared band.

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

[0005] The object of the present invention is to provide a phenoxazine derivative for preparing an anode material of an electrochromic device, a preparation method thereof, an anode material and an electrochromic medium composition. The embodiment of the present invention provides a new compound whose oxidation state absorption peak is located in the infrared band, which can then be used to prepare a near-infrared electrochromic device.

[0006] The present invention is achieved in that:

[0007] In a first aspect, the present invention provides a phenoxazine derivative for preparing an anode material for an electrochromic device, which is selected from the compounds shown in the structural formula:

[0008] Among them, R 1 -R 6 and R 8 -R 17 are independently selected from H or unsubstituted C1-C7 alkoxy, R 7 It is an unsubstituted C1-C10 alkyl group.

[0009] In a second aspect, the present invention provides an anode material for preparing an electrochromic device, wherein the raw material includes the phenoxazine derivative for preparing the anode material for an electrochromic device as described in any one of the aforementioned embodiments.

[0010] In a third aspect, the present invention provides an electrochromic medium composition, the raw materials of which include a cathode material and the anode material for preparing an electrochromic device described in the aforementioned embodiment.

[0011] In a fourth aspect, the present invention provides a method for preparing the phenoxazine derivative for preparing an anode material for an electrochromic device according to the aforementioned embodiment, wherein the synthesis is performed according to the following synthesis route:

[0012]

[0013] In a fifth aspect, the present invention provides an electrochromic device, which includes the electrochromic medium composition described in the aforementioned embodiment.

[0014] The present invention has the following beneficial effects: The embodiment of the present invention provides a new compound, the position of its oxidation state absorption peak is in the infrared band, and can be used to prepare near-infrared electrochromic devices, so that the electrochromic devices can achieve near-infrared regulation, and have great application potential in industries such as building windows, intelligent thermal regulation, filters and infrared military camouflage. DETAILED DESCRIPTION

[0015] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0016] In a first aspect, the present invention provides a phenoxazine derivative for preparing an anode material for an electrochromic device, which is selected from the compounds shown in the structural formula:

[0017] Among them, R 1 -R 6 and R 8 -R 17 Each is independently selected from H or unsubstituted C1-C7 alkoxy.

[0018] Specifically, R 1 -R 6 and R 8 -R 17 are independently selected from H or unsubstituted C1-C5 alkoxy; more preferably any one of H, methoxy and ethoxy. 10 and R15 is an unsubstituted C1-C7 alkoxy group, R 1 -R 6 , R 8 -R 9 , R 11 -R 14 and R 16 -R 17 is hydrogen; R 10 and R 15 is an unsubstituted C1-C5 alkoxy group, R 1 -R 6 , R 8 -R 9 , R 11 -R 14 and R 16 -R 17 is hydrogen. For example, the above-mentioned methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and other alkoxy groups.

[0019] R 7 It is an unsubstituted C1-C10 alkyl group; preferably an unsubstituted C1-C7 alkyl group; preferably an unsubstituted C1-C5 alkyl group, for example including but not limited to any one of methyl, ethyl and propyl.

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

[0021]

[0022] as well as

[0023] The above-mentioned phenoxazine derivatives for preparing anode materials of electrochromic devices are synthesized according to the following synthesis route:

[0024]

[0025] For example:

[0026]

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

[0028] In a third aspect, the present invention provides an anode material for preparing an electrochromic device, wherein the raw material includes the phenoxazine derivative for preparing the anode material for an electrochromic device as described in any one of the aforementioned embodiments.

[0029] The anode material may include only the above-mentioned phenoxazine derivatives, or may include other compounds.

[0030] In a third aspect, the present invention provides an electrochromic medium composition, the raw materials of which include a cathode material and the anode material for preparing an electrochromic device described in the aforementioned embodiment.

[0031] The cathode material can be selected from octyl viologen, or can be selected from 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, any value between 1:0.5, 1:1, 1:1.5, etc., and 1:(0.5-1.5).

[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] In a fifth aspect, the present invention provides an electrochromic device, which includes the electrochromic medium composition described in the aforementioned embodiment.

[0035] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0036] Example 1

[0037] The present invention provides a phenoxazine derivative, the structural formula of which is shown below:

[0038]

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

[0040] Step 1: Add phenoxazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol) and tetrahydrofuran to a three-necked flask, heat to 70 ° C, then add iodomethane (6.81 g, 48 mmol) to react for 12 hours. After the reaction is completed, water is added to cool it, and then dichloromethane is added for extraction, and the obtained organic phase is rotary evaporated. After spin drying, petroleum ether is added, and then filtered, the filtrate is collected, and 10-methyl-10H-phenoxazine (6.46 g, yield 82%) is obtained after drying.

[0041] Step 2: Add 10-methyl-10H-phenoxazine (6.46 g, 32.75 mmol) and tetrahydrofuran to a three-necked flask, cool to 0°C, then add N-bromosuccinimide (11.66 g, 65.50 mmol) in small amounts and several times. Stop the reaction when the color of the system becomes lighter, then add a small amount of sodium dithionite to quench, and then use water and dichloromethane for extraction. The obtained organic phase is rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, yield 80%).

[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 then nitrogen was bubbled for 20 min, and tetrakis(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the temperature was raised to 110°C, and the reaction was carried out for 16 h. After the reaction was completed, the organic phase was extracted with water and dichloromethane, and the obtained organic phase was rotary evaporated, and then separated using a silica gel column (developing agent 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 of 3,7-bis(4-methoxyphenyl)-10-methyl-10H-phenoxazine are as follows:

[0044] 1 H NMR (C 6 D 6 ,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), 7.10 (m, J=8.6Hz, 2H, Ar-H), 6.78 (s, J=7.3Hz, 4H, Ar-H), 3.32 (m, J=7.1Hz, 6H, -CH 3 ), 2.72 (s, J=6.7Hz, 3H, -CH 3 ).

[0045] Example 2

[0046] The present invention provides a phenoxazine derivative, the structural formula of which is shown below:

[0047]

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

[0049] Step 1: Add phenoxazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol) and tetrahydrofuran to a three-necked flask, heat to 70 ° C, then add iodoethane (7.48 g, 48 mmol) to react for 12 hours. After the reaction is completed, water is added to cool it, and then dichloromethane is added for extraction, and the obtained organic phase is rotary evaporated. After rotary drying, petroleum ether is added, and then filtered, the filtrate is collected, and 10-ethyl-10H-phenoxazine (67.01 g, yield 83%) is obtained after drying.

[0050] Step 2: Add 10-ethyl-10H-phenoxazine (6.46 g, 30.6 mmol) and tetrahydrofuran to a three-necked flask, cool to 0°C, then add N-bromosuccinimide (11.66 g, 66.4 mmol) in small amounts and several times. Stop the reaction when the color of the system becomes lighter, then add a small amount of sodium dithionite to quench, and then use water and dichloromethane for extraction. The obtained organic phase is rotary evaporated and dried to obtain the product 3,7-dibromo-10-ethyl-10H-phenoxazine (9.03 g, yield 80%).

[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 then nitrogen was bubbled for 20 min, and tetrakis(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the temperature was raised to 110°C, and the reaction was carried out for 16 h. After the reaction was completed, the organic phase was extracted with water and dichloromethane, and the obtained organic phase was rotary evaporated, and then separated using a silica gel column (developing agent 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 of 3,7-bis(4-methoxyphenyl)-10-ethyl-10H-phenoxazine are as follows:

[0053] 1 H NMR (C 6 D 6 ,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, -CH 3), 2.32(d, J=6.2Hz, 2H, -CH 2 ), 1.38 (m, J=6.7Hz, 3H, -CH 3 ).

[0054] Example 3

[0055] The present invention provides a phenoxazine derivative, the structural formula of which is shown below:

[0056]

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

[0058] Step 1: Add phenoxazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol) and tetrahydrofuran to a three-necked flask, heat to 70 ° C, then add iodomethane (6.81 g, 48 mmol) to react for 12 hours. After the reaction is completed, water is added to cool it, and then dichloromethane is added for extraction, and the obtained organic phase is rotary evaporated. After spin drying, petroleum ether is added, and then filtered, the filtrate is collected, and 10-methyl-10H-phenoxazine (6.46 g, yield 82%) is obtained after spin drying.

[0059] Step 2: Add 10-methyl-10H-phenoxazine (6.46 g, 35.30 mmol) and tetrahydrofuran to a three-necked flask, cool to 0°C, then add N-bromosuccinimide (11.66 g, 65.50 mmol) in small amounts and several times. Stop the reaction when the color of the system becomes lighter, then add a small amount of sodium dithionite to quench, and then use water and dichloromethane for extraction. The obtained organic phase is rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, yield 80%).

[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 then nitrogen was bubbled for 20 min, and tetrakis(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the temperature was raised to 110°C, and the reaction was carried out for 16 h. After the reaction, the organic phase was extracted with water and dichloromethane, and the obtained organic phase was rotary evaporated, and then separated by a silica gel column (developing agent 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 of the above 3,7-bis(4-ethoxyphenyl)-10-methyl-10H-phenoxazine are as follows:

[0062] 1 H NMR (C 6 D 6 ,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, -CH 2 ), 3.31 (m, J=7.3Hz, 3H, -CH 3 ), 1.74 (s, J=6.9Hz, 6H, -CH 3 ).

[0063] Example 4

[0064] The present invention provides a phenoxazine derivative, the structural formula of which is shown below:

[0065]

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

[0067] Step 1: Add phenoxazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol) and tetrahydrofuran to a three-necked flask, heat to 70 ° C, then add iodoethane (7.48 g, 48 mmol) to react for 12 hours. After the reaction is completed, add water to cool it, then add dichloromethane to extract, and the obtained organic phase is rotary evaporated. After rotary drying, petroleum ether is added, and then filtered, the filtrate is collected, and 10-ethyl-10H-phenoxazine (7.01 g, yield 83%) is obtained after drying.

[0068] Step 2: Add 10-ethyl-10H-phenoxazine (6.46 g, 30.6 mmol) and tetrahydrofuran to a three-necked flask, cool to 0°C, then add N-bromosuccinimide (11.66 g, 66.4 mmol) in small amounts and several times. Stop the reaction when the color of the system becomes lighter, then add a small amount of sodium dithionite to quench, and then use water and dichloromethane for extraction. The obtained organic phase is rotary evaporated and dried to obtain the product 3,7-dibromo-10-ethyl-10H-phenoxazine (9.03 g, yield 80%).

[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 then nitrogen was bubbled for 20 min, and tetrakis(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the temperature was raised to 110°C, and the reaction was carried out for 16 h. After the reaction was completed, the organic phase was extracted with water and dichloromethane, and the obtained organic phase was subjected to rotary evaporation, and then separated using a silica gel column (developing agent 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 of the above 3,7-bis(4-ethoxyphenyl)-10-ethyl-10H-phenoxazine are as follows:

[0071] 1 H NMR (C 6 D 6 ,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), 6.77 (s, J=7.1Hz, 4H, Ar-H), 4.30 (d, J=7.5Hz, 4H, -CH 2 ), 2.34(d, J=6.8Hz, 2H, -CH 2 ), 1.76 (s, J=7.2Hz, 6H, -CH 3 ), 1.37 (m, J=7.3Hz, 3H, -CH 3 ).

[0072] Comparative Example 1

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

[0074]

[0075] The preparation method is as follows:

[0076] Step 1: Add phenoxazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol) and tetrahydrofuran to a three-necked flask, heat to 70 ° C, then add iodomethane (6.81 g, 48 mmol) to react for 12 hours. After the reaction is completed, water is added to cool it, and then dichloromethane is added for extraction, and the obtained organic phase is rotary evaporated. After spin drying, petroleum ether is added, and then filtered, the filtrate is collected, and 10-methyl-10H-phenoxazine (6.46 g, yield 82%) is obtained after drying.

[0077] Step 2: Add 10-methyl-10H-phenoxazine (6.46 g, 35.30 mmol) and tetrahydrofuran to a three-necked flask, cool to 0°C, then add N-bromosuccinimide (11.66 g, 65.50 mmol) in small amounts and several times. Stop the reaction when the color of the system becomes lighter, then add a small amount of sodium dithionite to quench, and then use water and dichloromethane for extraction. The obtained organic phase is rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, yield 80%).

[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 then nitrogen was bubbled for 20 min, and tetrakis(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the temperature was raised to 110°C, and the reaction was carried out for 16 h. After the reaction was completed, the organic phase was extracted with water and dichloromethane, and the obtained organic phase was rotary evaporated, and then separated by a silica gel column (developing agent 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 of the above 3-bromo-7-(4-ethoxyphenyl)-10-methyl-10H-phenoxazine (3.23 g, yield 48%) are as follows:

[0080] 1 H NMR (DMSO-d 6 ,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, -CH 2 ), 3.20(s, 3H, -CH 3 ), 1.34 (t, J=6.2Hz, 3H, -CH 3).

[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 the phenoxazine derivative is as follows:

[0085] Step 1: Add phenoxazine (7.32 g, 40 mmol), potassium tert-butoxide (5.38 g, 48 mmol) and tetrahydrofuran to a three-necked flask, heat to 70 ° C, then add iodomethane (6.81 g, 48 mmol) to react for 12 hours. After the reaction is completed, water is added to cool it, and then dichloromethane is added for extraction, and the obtained organic phase is rotary evaporated. After spin drying, petroleum ether is added, and then filtered, the filtrate is collected, and 10-methyl-10H-phenoxazine (6.46 g, yield 82%) is obtained after drying.

[0086] Step 2: Add 10-methyl-10H-phenoxazine (6.46 g, 35.30 mmol) and tetrahydrofuran to a three-necked flask, cool to 0°C, then add N-bromosuccinimide (11.66 g, 65.50 mmol) in small amounts and several times. Stop the reaction when the color of the system becomes lighter, then add a small amount of sodium dithionite to quench, and then use water and dichloromethane for extraction. The obtained organic phase is rotary evaporated and dried to obtain the product 3,7-dibromo-10-methyl-10H-phenoxazine (9.30 g, yield 80%).

[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 then nitrogen was bubbled for 20 min, and then tetrakis(triphenylphosphine)palladium (0.36 g, 0.3 mmol) was added, and the temperature was raised to 110°C, and the reaction was carried out for 16 h. After the reaction was completed, the organic phase was extracted with water and dichloromethane, and the obtained organic phase was rotary evaporated, and then separated using a silica gel column (developing agent 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 of the above 3-bromo-7-(2-ethoxyphenyl)-10-methyl-10H-phenoxazine (3.23 g, yield 48%) are as follows:

[0089] 1H NMR (DMSO-d 6 ,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, -CH 2 ), 3.20(s, 3H, -CH 3 ), 1.55 (t, J=6.2Hz, 3H, -CH 3 ).

[0090] Test Example 1

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

[0092] Test Example 2

[0093] The above compounds (anode material) and octyl viologen (cathode material) were mixed and dissolved in propylene carbonate to obtain an electrochromic medium, wherein 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, wherein the properties and transmittance data in different bands when a voltage of 1.0 V to 2.0 V is applied are shown in Table 1.

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

[0096]

[0097] According to Table 1, the embodiments of the present invention reduce the redox potential by introducing an alkyl group on N and an alkoxy electron-donating group on the benzene ring, wherein the longer the alkyl chain, the stronger the electron-donating ability, the more obvious the potential reduction, and the lower the transmittance in the infrared band. Compared with embodiments 1-4, comparative examples 1 and 2 lack the conjugation of a benzene ring and have almost no response in the near-infrared band. This shows that the phenoxazine derivatives provided in the embodiments of the present invention can realize the near-infrared regulation of electrochromic devices, and have great application potential in industries such as building windows, intelligent thermal regulation, filters, and infrared military camouflage.

[0098] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. 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. A phenoxazine derivative for preparing an anode material for an electrochromic device, characterized in that: It is selected from the compounds shown in the structural formula: Among them, R1-R6 and R8-R 17 are independently selected from H or unsubstituted C1-C7 alkoxy, and R7 is unsubstituted C1-C10 alkyl.

2. The phenoxazine derivative for preparing an anode material for an electrochromic device according to claim 1, characterized in that: R1-R6 and R8-R 17 Each is independently selected from H or unsubstituted C1-C5 alkoxy; more preferably any one of H, methoxy and ethoxy.

3. The phenoxazine derivative for preparing an anode material for an electrochromic device according to claim 1, characterized in that: R 10 and R 15 is an unsubstituted C1-C7 alkoxy group, R1-R6, R8-R 9、 R 11 -R 14 and R 16 -R 17 is hydrogen; Preferably, R 10 and R 15 is an unsubstituted C1-C5 alkoxy group, R1-R6, R8-R 9、 R 11 -R 14 and R 16 -R 17 For hydrogen.

4. The phenoxazine derivative for preparing an anode material for an electrochromic device according to claim 1, characterized in that: R7 is an unsubstituted C1-C7 alkyl group; preferably an unsubstituted C1-C5 alkyl group, and more preferably any one of a methyl group, an ethyl group and a propyl group.

5. The phenoxazine derivative for preparing an anode material for an electrochromic device according to claim 1, characterized in that: The phenoxazine derivative is selected from any one of the compounds represented by the following structural formulas: as well as 6. An anode material for preparing an electrochromic device, characterized in that: The raw materials include the phenoxazine derivative for preparing the anode material of the electrochromic device as described in any one of claims 1 to 5.

7. An electrochromic medium composition, characterized in that: The raw materials include cathode materials and the anode material for preparing the electrochromic device as claimed in claim 6.

8. The electrochromic medium composition according to claim 7, characterized in that: The concentrations of the cathode material and the anode material in the electrochromic medium composition are 1-100 mM, preferably 10-50 mM, respectively; Preferably, 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 for an electrochromic device according to claim 1, characterized in that: The synthesis was carried out according to the following synthesis route:

10. An electrochromic device, characterized in that: The invention comprises the phenoxazine derivative for preparing anode materials of electrochromic devices as claimed in claim 1.

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