A benzotriazine diradical compound, its preparation method, and its application in organic resistive switching memory, near-infrared detectors, and temperature-controlled films.

Abstract

This invention belongs to the field of new materials technology, specifically relating to a benzotriazine diradical compound, its preparation method, and its applications in organic resistive switching memory (RSM), near-infrared detectors, and temperature-controlled films. The benzotriazine diradical organic magnetic compound prepared by this invention possesses excellent magnetic properties, reversible redox characteristics, and film-forming properties, making it suitable for use in organic RSM. Furthermore, it exhibits good thermal stability and excellent photothermal conversion capabilities, making it applicable to near-infrared detectors and temperature-controlled films. The prepared organic RSM demonstrates excellent storage performance; the prepared near-infrared detector exhibits ultra-high electro-response efficiency; and the prepared temperature-controlled film provides excellent temperature control and energy-saving effects.

Description

Technical Field

[0001] This invention belongs to the field of new materials technology, specifically relating to a benzotriazine diradical compound, its preparation method, and its application in organic resistive switching memory, near-infrared detectors, and temperature-controlled films. Background Technology

[0002] Biradical molecules represent an important interdisciplinary field encompassing synthetic chemistry, functional materials, and nanotechnology. Delocalized biradicals can be classified into quinone and non-quinone structures. Generally, molecules with two radicals in a para-position are quinone structures, exhibiting opposite spin directions. Quinone molecules are widely studied due to their low band gap energy, bipolar characteristics, long-wavelength absorption, convertible spin states, and conductive properties. Compared to other types of radicals, blatter radicals possess unique electrical and magnetic properties, such as antiferromagnetic or ferromagnetic interactions, spin π delocalization, a narrow electrochemical window, and low excitation energy. They also have well-established synthetic routes and extremely high stability. Furthermore, blatter radicals have the unique advantage of high structural modifiability. They possess three aromatic sites that can modulate molecular properties. However, current molecular structures based on blitter radicals suffer from several drawbacks, including weak absorption across various optical bands, limited detection range in the near-infrared region, insufficient photothermal performance, unsystematic application research, gaps in research on electronic devices, and untapped potential value. Therefore, designing and synthesizing several molecules to introduce bis-blitter radicals to narrow the band gap of organic conjugated molecules is crucial to improving photothermal conversion efficiency, achieving high absorption in the near-infrared region, and making breakthroughs in the storage field based on single-radical structures. Summary of the Invention

[0003] In view of the problems and shortcomings of the existing technology, the purpose of this invention is to provide a benzotriazine diradical compound, its preparation method and its application in organic resistive switching memory, near-infrared detector and temperature control film.

[0004] To achieve the objectives of this invention, the technical solution adopted is as follows:

[0005] The first aspect of this invention provides a benzotriazine diradical compound, the structural formula of which is shown in Formula 1:

[0006]

[0007] Wherein, R is selected from cyano, nitro, and -O-(CH2). n Either CH3 or -CH2CH3, where n is 0, 4, or 9.

[0008] A second aspect of this invention provides a method for preparing the benzotriazine diradical compound described in the first aspect, comprising the following steps:

[0009] S1: Add compound A and compound B to tetrahydrofuran and mix well. Then add triethylamine and heat under reflux at 85℃~90℃ for 24h~48h to separate the intermediate product.

[0010] S2: Dissolve the intermediate product obtained in step S1 in a small amount of dichloromethane, then add a large amount of ethanol, pass air through, and simultaneously add 1,8-diazabicyclo[5.4.0]undec-7-ene. Stir the reaction while bubbling. After the reaction is complete, filter and wash the filter cake with ethyl acetate to obtain the benzotriazine diradical compound shown in Formula 1.

[0011] Wherein, the structural formula of compound A is selected from any one of formulas a-1, a-2, a-3, a-4, a-5, and a-6:

[0012]

[0013] The structural formula of compound B is shown in formula b:

[0014]

[0015] Preferably, in step S1, the molar ratio of compound A to compound B is (2-3):1; the molar ratio of triethylamine to compound A is (1-3):1; and in step S2, the molar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene to compound A is 1:(1-2).

[0016] Preferably, after the reaction in step S1 is completed, the reaction solution is cooled to room temperature, filtered, and the filtrate is collected; the solvent in the filtrate is removed by rotary evaporation under reduced pressure to obtain the intermediate product.

[0017] Furthermore, compound A is prepared by the following method:

[0018] Compound C and triphenylphosphine were added to acetonitrile, followed by carbon tetrachloride, and the mixture was stirred at room temperature. After the reaction was complete, the mixture was filtered, and the filtrate was purified to obtain compound A. The structural formula of compound C is selected from any one of formulas c-1, c-2, c-3, c-4, c-5, and c-6.

[0019]

[0020]

[0021] The molar ratio of compound C to triphenylphosphine is 1:(1-2), and the molar ratio of carbon tetrachloride to compound C is (1-2):1.

[0022] Compound C is obtained by amidation reaction of compound D and compound E. The specific preparation method is as follows: compound E and triethylamine are added to tetrahydrofuran, stirred in an ice-water bath for 10-15 minutes, then compound D is added to obtain a mixed solution; the mixture is naturally heated to room temperature and stirred for 18-24 hours; after the reaction is complete, the mixture is filtered, the filtrate is collected, the solvent is evaporated to obtain a solid product, and the solid product is purified to obtain compound C. The structural formula of compound D is selected from any one of formulas d-1, d-2, d-3, d-4, d-5, and d-6, and the structural formula of compound E is shown in formula e.

[0023]

[0024] The third aspect of this invention provides the application of the benzotriazine diradical compounds described in the first aspect above in the preparation of organic resistive switching memory, near-infrared detectors, and temperature-controlled films.

[0025] The organic resistive switching memory includes a base layer, an organic active layer, and a top electrode layer, wherein the organic active layer is prepared from any one of the benzotriazine diradical compounds described in the first aspect above.

[0026] The near-infrared detector includes a support group and a response group, wherein the response group is prepared by uniformly dispersing any one of the benzotriazine diradical compounds described in the first aspect above in an ionic liquid.

[0027] The temperature-controlled film is a thin film prepared by adding the aforementioned benzotriazine diradical compound to a necessary film-forming material. The film-forming material is preferably PU. Furthermore, by enclosing multiple support plates to form sidewalls and covering the top with the temperature-controlled film containing the aforementioned benzotriazine diradical compound, an energy-saving house can be manufactured and further applied in thermal management.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] 1. This invention successfully prepared benzotriazine diradical compounds. By introducing bis-Blatter radicals, the band gap of the organic conjugated molecule is narrowed. The ground-state structure is contributed by both the closed-shell quinone form and the open-shell diradical, endowing the material with a certain degree of diradical properties. The benzotriazine diradical organic magnetic compounds prepared by this invention exhibit good magnetic properties, reversible redox characteristics, and film-forming properties, making them suitable for use in organic resistive switching memories. Furthermore, they possess good thermal stability and excellent photothermal conversion capabilities, making them suitable for use in near-infrared detectors and temperature-controlled films.

[0030] 2. The method for preparing benzotriazine diradical compounds provided by this invention is simple, reduces time costs, and uses inexpensive and readily available raw materials, thus providing a new approach for the preparation of diradicals.

[0031] 3. The organic resistive switching memory based on benzotriazine diradical compounds provided by this invention has good storage performance and is of guiding significance for exploring the application of quinone conjugated diradicals in the field of memory.

[0032] 4. The near-infrared detector based on benzotriazine diradical compounds provided by this invention has ultra-high electrical response efficiency and has potential application value in the field of near-infrared detection.

[0033] 5. The temperature control film based on benzotriazine diradical compounds provided by this invention has excellent temperature control and energy-saving effects, and has extremely high application value in the field of energy conservation and environmental protection. Attached Figure Description

[0034] Figure 1 For compound A with the structural formula shown in formula a-3 1 HNMR spectrum;

[0035] Figure 2 For compound C with the structural formula shown in formula c-3 1 HNMR spectrum;

[0036] Figure 3 For compound A with the structural formula shown in formula a-5 1 HNMR spectrum;

[0037] Figure 4 For compound C with the structural formula shown in formula c-5 1 HNMR spectrum;

[0038] Figure 5 The mass spectrum of a benzotriazine diradical compound with the structural formula shown in Formula 7 is shown.

[0039] Figure 6 The mass spectrum of a benzotriazine diradical compound with the structural formula shown in Formula 8 is shown.

[0040] Figure 7 The mass spectrum of a benzotriazine diradical compound with the structural formula shown in Formula 9 is shown.

[0041] Figure 8 The mass spectrum of a benzotriazine diradical compound with the structural formula shown in Formula 10 is shown.

[0042] Figure 9 The mass spectrum of a benzotriazine diradical compound with the structural formula shown in Formula 11 is shown.

[0043] Figure 10 The mass spectrum of a benzotriazine diradical compound with the structural formula shown in Formula 12 is shown.

[0044] Figure 11The ultraviolet spectra of the five benzotriazine diradical compounds prepared in Examples 7-12 are shown below.

[0045] Figure 12 Infrared spectra of the five benzotriazine diradical compounds prepared in Examples 7-12;

[0046] Figure 13 Cyclic voltammetry diagrams of the five benzotriazine diradical compounds prepared in Examples 7-12;

[0047] Figure 14 Thermogravimetric analysis (TGA) diagrams of the benzotriazine diradical compounds prepared in Examples 7-12 are shown.

[0048] Figure 15 The images show the photothermal properties of the benzotriazine diradical compounds prepared in Examples 7-12.

[0049] Figure 16 ESR diagrams of the benzotriazine diradical compounds prepared in Examples 7-12;

[0050] Figure 17 This is a structural diagram of the near-infrared detector prepared in Example 14;

[0051] Figure 18 The test process and electrical response performance of the near-infrared detector prepared in Example 14 are shown in the figure.

[0052] Figure 19 This is a structural diagram of the organic resistive switching memory prepared in Example 16;

[0053] Figure 20 The image shows the polarized morphology of the thin film of the benzotriazine diradical compound prepared in Example 12.

[0054] Figure 21 The GIWAXS characterization diagram of the benzotriazine diradical compound prepared in Example 12 is shown below.

[0055] Figure 22 IV characteristic curve of the organic resistive switching memory prepared in Example 16;

[0056] Figure 23 A structural diagram of the energy-saving house prepared in Example 18;

[0057] Figure 24 Transmittance diagram of the temperature control film in the energy-saving house prepared in Example 18;

[0058] Figure 25 Indoor temperature diagram of the energy-saving house prepared in Example 18 under simulated sunlight;

[0059] Figure 26The indoor temperature of the energy-saving house prepared for Example 18 under natural sunlight for one day. Detailed Implementation

[0060] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0061] Example 1

[0062] A method for preparing compound A with the structural formula shown in formula a-1, comprising the following specific steps:

[0063] (1) Add 5g (1eq) of compound C and 7.72g (1.25eq) of triphenylphosphine to 100mL of anhydrous acetonitrile, then add 2.84mL (1.25eq) of anhydrous carbon tetrachloride, and stir overnight at room temperature;

[0064] (2) After the reaction is complete, if a product is precipitated, wash the bottle with cold acetonitrile solution, filter and collect the product, and then purify the filtrate by silica gel column chromatography using petroleum ether as the eluent. Collect the eluent, remove the solvent by vacuum evaporation, and combine the obtained product with the filtered product to obtain compound A.

[0065] The structural formula of compound C is shown in formula c-1, and its name is 4-Cyanobenzoic acid 2-phenylhydrazide, with CAS number 88405-47-4; the structural formula of compound A is shown in formula a-1, and its name is 4-Cyano-N-phenylbenzenecarbohydrazonoyl chloride, with CAS number 50656-04-7.

[0066]

[0067] The reaction equation for preparing compound A, which has the structural formula as shown in formula a-1, is as follows:

[0068]

[0069] The preparation method of compound C, whose structural formula is shown in formula c-1, is as follows:

[0070] 4.55 mL of compound E was added to tetrahydrofuran, followed by 12.86 mL (2 eq) of triethylamine to obtain a mixed solution. The mixture was stirred in an ice-water bath for 10 minutes. Then, 10 mL of 8.39 g (1.1 eq) of compound D dissolved in tetrahydrofuran was added dropwise to the mixture while maintaining the ice-water bath conditions. After the addition was complete, the mixture was allowed to cool to room temperature naturally and stirred for 24 hours. After the reaction was complete, the mixture was filtered, and the filtrate was collected. The filtrate was then evaporated under reduced pressure to remove the solvent and recrystallized to obtain compound C.

[0071] The structural formula of compound E is shown in formula e, and its name is phenylhydrazine with CAS number 100-63-0; the structural formula of compound D is shown in formula d-1, and its name is 4-Cyanobenzoyl chloride with CAS number 6068-72-0.

[0072]

[0073] The reaction equation for preparing compound C, whose structural formula is shown in formula c-1, is as follows:

[0074]

[0075] Example 2

[0076] A compound A, with the structural formula shown in formula a-2, is named 4-Nitro-N-phenylbenzenecarbohydrazonoyl chloride and has the CAS number 20147-55-1.

[0077]

[0078] The preparation method of compound A with the structural formula shown in formula a-2 described in this embodiment is basically the same as that of compound A with the structural formula shown in formula a-1 in Example 1. The difference is that the structural formula of compound C in this embodiment is shown in formula c-2, the substance name is 4-Nitrobenzoic acid 2-phenylhydrazide, and the CAS number is 39718-99-5.

[0079]

[0080] The preparation method of compound C, whose structural formula is shown in formula c-2, is basically the same as that of compound C in Example 1. The difference is that the structural formula of compound D in this example is shown in formula d-2, the substance name is 4-Nitrobenzoyl chloride, and the CAS number is 122-04-3.

[0081]

[0082] Example 3

[0083] A compound A, with the structural formula shown in formula a-3, is named Benzenecarbohydrazonoylchloride,4-ethyl-N-phenyl-,[C(Z)]-, and has the CAS number 3058697-47-2.

[0084]

[0085] The preparation method of compound A with the structural formula shown in formula a-3 described in this embodiment is basically the same as that of compound A with the structural formula shown in formula a-1 in Example 1. The difference is that the structural formula of compound C in this embodiment is shown in formula c-3, the substance name is 4-Ethylbenzoic acid 2-phenylhydrazide, and the CAS number is 1624221-93-7.

[0086]

[0087] The preparation method of compound C, whose structural formula is shown in formula c-3, is basically the same as that of compound C in Example 1. The difference is that the structural formula of compound D in this example is shown in formula d-3, the substance name is 4-Ethylbenzoyl chloride, and the CAS number is 16331-45-6.

[0088]

[0089] NMR analysis was performed on compound A (NMR results are shown in the figure). Figure 1 (as shown) 1 ¹H NMR (400MHz, Chloroform-d) δ 8.00 (s, 1H), 7.87–7.80 (m, 2H), 7.35–7.27 (m, 2H), 7.25–7.21 (m, 2H), 7.20–7.13 (m, 2H), 6.93 (tt, J = 7.3, 1.2Hz, 1H), 2.69 (q, J = 7.6Hz, 2H), 1.26 (t, J = 7.6Hz, 3H). These results confirm that the obtained product is the target product.

[0090] NMR analysis was performed on the prepared compound C (NMR results are shown in the figure). Figure 2 (as shown) 1 ¹H NMR (400MHz, Chloroform-d) δ 8.07 (s, 1H), 7.79–7.73 (m, 2H), 7.32–7.19 (m, 5H), 6.92 (td, J = 7.6, 1.1Hz, 3H), 2.71 (q, J = 7.6Hz, 2H), 1.26 (t, J = 7.6Hz, 3H). These results confirm that the obtained product is the target product.

[0091] Example 4

[0092] A compound A, with the structural formula shown in formula a-4, is named 4-Methoxy-N-phenylbenzenecarbohydrazonoyl chloride and has the CAS number 40277-63-2.

[0093]

[0094] The preparation method of compound A with the structural formula shown in formula a-4 described in this embodiment is basically the same as that of compound A with the structural formula shown in formula a-1 in Example 1. The difference is that the structural formula of compound C in this embodiment is shown in formula c-4, the substance name is Benzoic acid, 4-methoxy-, 2-phenylhydrazide, and the CAS number is 15089-03-9.

[0095]

[0096] The preparation method of compound C, whose structural formula is shown in formula c-4, is basically the same as that of compound C in Example 1. The difference is that the structural formula of compound D in this example is shown in formula d-4, the substance name is 4-Methoxybenzoyl chloride, and the CAS number is 100-07-2.

[0097]

[0098] Example 5

[0099] A compound A with the structural formula shown in formula a-5:

[0100]

[0101] The preparation method of compound A, with structural formula a-5, in this embodiment is basically the same as that of compound A, with structural formula a-1, in Example 1. The difference is that the structural formula of compound C in this embodiment is shown in formula c-5.

[0102]

[0103] The preparation method of compound C, whose structural formula is shown in formula c-5, is basically the same as that of compound C in Example 1, except that: in this example, the structural formula of compound D is shown in formula d-5, the substance name is 4-Pentyloxybenzoyl chloride, and the CAS number is 36823-84-4.

[0104]

[0105] NMR analysis was performed on compound A (NMR results are shown in the figure). Figure 3 (as shown) 1 ¹H NMR (400MHz, Chloroform-d) δ 7.93 (s, 1H), 7.87–7.80 (m, 2H), 7.33–7.25 (m, 2H), 7.19–7.12 (m, 2H), 6.95–6.88 (m, 3H), 3.99 (tt, J = 6.6Hz, 2H), 1.81 (dq, J = 8.0, 6.6Hz, 2H), 1.51–1.32 (m, 4H), 0.94 (t, J = 7.1Hz, 3H). These results confirm that the obtained product is the target product.

[0106] NMR analysis was performed on the prepared compound C (NMR results are shown in the figure). Figure 4 (as shown) 1 ¹H NMR (400MHz, Chloroform-d) δ 8.16 (s, 1H), 7.82–7.73 (m, 2H), 7.21 (t, J = 7.8Hz, 2H), 6.93–6.85 (m, 5H), 4.93 (s, 1H), 3.99 (t, J = 6.6Hz, 2H), 1.86–1.75 (m, 2H), 1.49–1.32 (m, 4H), 0.94 (t, J = 7.0Hz, 2H). These results confirm that the obtained product is the target product.

[0107] Example 6

[0108] A compound A, with the structural formula shown in formula a-6, is named Benzenecarbohydrazonoylchloride, 4-(decyloxy)-N-phenyl-, and has the CAS number 2923971-64-4.

[0109]

[0110] The preparation method of compound A with the structural formula shown in formula a-6 described in this embodiment is basically the same as that of compound A with the structural formula shown in formula a-1 in Example 1. The difference is that the structural formula of compound C in this embodiment is shown in formula c-6, the substance name is Benzoic acid, 4-(decyloxy)-, 2-phenylhydrazide, and the CAS number is 2923971-66-6.

[0111]

[0112] The preparation method of compound C, whose structural formula is shown in formula c-6, is basically the same as that of compound C in Example 1. The difference is that the structural formula of compound D in this example is shown in formula d-6, the substance name is 4-(Decyloxy)benzoyl chloride, and the CAS number is 50625-44-0.

[0113]

[0114] Example 7

[0115] A benzotriazine diradical compound, the structural formula of which is shown in Formula 1-1:

[0116]

[0117] The specific steps for preparing the above-mentioned benzotriazine diradical compounds are as follows:

[0118] S1: Compound B (0.3 g, 1.896 mmol) and compound A (1.2 g, 2.5 eq) were added to 40 mL of anhydrous tetrahydrofuran to obtain a mixed solution. 1.8 mL of triethylamine was added to the mixed solution, and the mixture was refluxed at 85 °C for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature and filtered. The filtrate was collected and the solvent was removed by vacuum evaporation to obtain the intermediate product.

[0119] Wherein, compound B is as shown in formula b, the substance name is naphthalene-2,6-diamine, the CAS number is 2243-67-6, and compound A is compound A prepared in Example 1 with the structural formula shown in formula a-1.

[0120]

[0121] S2: Dissolve the intermediate product (1 eq) in anhydrous dichloromethane (20 mL) and add a large amount of ethanol (120 mL). Add 1,8-diazabicyclo[5.4.0]undec-7-ene (2 eq), purge with air, and stir the reaction under bubbling. After the reaction is complete, filter and wash the filter cake with ethyl acetate to obtain the target product compound.

[0122] The specific overall reaction equation is as follows:

[0123]

[0124] The benzotriazine diradical compounds prepared in this embodiment were analyzed by mass spectrometry, and the results are as follows: Figure 5 As shown, the C1 of HRMS(ESI+):[MH]+ was analyzed by mass spectrometry. 38 H 22 N8 2The calculated value is 590.3685, and the obtained value is 590.1967. The above results confirm that the obtained product is the target product.

[0125] Example 8

[0126] A benzotriazine diradical compound, the structural formula of which is shown in Formula 1-2:

[0127]

[0128] The preparation method of the benzotriazine free radical compound described in this embodiment is basically the same as that in Example 7, except that in step S1, the compound A is the compound A with the structural formula shown in Formula a-2 prepared in Example 2 (the amount of compound A remains unchanged).

[0129] The benzotriazine diradical compounds prepared in this embodiment were analyzed by mass spectrometry, and the results are as follows: Figure 6 As shown, the C1 of HRMS(ESI+):[MH]+ was analyzed by mass spectrometry. 36 H 22 N8O4 2 The calculated value is 630.1764, and the obtained value is 629.9778. The above results confirm that the obtained product is the target product.

[0130] Example 9

[0131] A benzotriazine diradical compound, the structural formula of which is shown in Formulas 1-3:

[0132]

[0133] The preparation method of the benzotriazine free radical compound described in this embodiment is basically the same as that in Example 7, except that in step S1, the compound A is the compound A with the structural formula shown in Formula a-3 prepared in Example 3 (the amount of compound A remains unchanged).

[0134] The benzotriazine diradical compounds prepared in this embodiment were analyzed by mass spectrometry, and the results are as follows: Figure 7 As shown, the C1 of HRMS(ESI+):[MH]+ was analyzed by mass spectrometry. 40 H 32 N6 2 The calculated value is 596.2688, and the obtained value is 596.1564. The above results confirm that the obtained product is the target product.

[0135] Example 10

[0136] A benzotriazine diradical compound, the structural formula of which is shown in Formulas 1-4:

[0137]

[0138] The preparation method of the benzotriazine free radical compound described in this embodiment is basically the same as that in Example 7, except that in step S1, the compound A is the compound A with the structural formula shown in Formula a-4 prepared in Example 4 (the amount of compound A remains unchanged).

[0139] The benzotriazine diradical compounds prepared in this embodiment were analyzed by mass spectrometry, and the results are as follows: Figure 8 As shown, the C1 of HRMS(ESI+):[MH]+ was analyzed by mass spectrometry. 38 H 28 N6O2 2· The calculated value is 600.2274, and the obtained value is 600.0906. The above results confirm that the obtained product is the target product.

[0140] Example 11

[0141] A benzotriazine diradical compound, the structural formula of which is shown in Formulas 1-5:

[0142]

[0143] The preparation method of the benzotriazine free radical compound described in this embodiment is basically the same as that in Example 7, except that in step S1, the compound A is the compound A with the structural formula shown in Formula a-5 prepared in Example 5 (the amount of compound A remains unchanged).

[0144] The benzotriazine diradical compounds prepared in this embodiment were analyzed by mass spectrometry, and the results are as follows: Figure 9 As shown, the C1 of HRMS(ESI+):[MH]+ was analyzed by mass spectrometry. 46 H 44 N6O2 2· The calculated value is 712.3529, and the obtained value is 712.8491. The above results confirm that the obtained product is the target product.

[0145] Example 12

[0146] A benzotriazine diradical compound, the structural formula of which is shown in Formulas 1-6:

[0147]

[0148] The preparation method of the benzotriazine free radical compound described in this embodiment is basically the same as that in Example 7, except that in step S1, the compound A is the compound A with the structural formula shown in Formula a-6 prepared in Example 6 (the amount of compound A remains unchanged).

[0149] The benzotriazine diradical compounds prepared in this embodiment were analyzed by mass spectrometry, and the results are as follows: Figure 10 As shown, the C1 of HRMS(ESI+):[MH]+ was analyzed by mass spectrometry. 56 H 64 N6O2 2· The calculated value is 852.5091, and the obtained value is 852.4959. The above results confirm that the obtained product is the target product.

[0150] Example 13 Product Characterization and Performance Testing

[0151] The benzotriazine diradical compounds prepared in Examples 7-12 were named NCN-D, NNO2-D, NEt-D, NMeO-D, NPeO-D, and NDeO-D, respectively, and their performance was characterized.

[0152] (I) Optical Characterization

[0153] (1) Ultraviolet-absorption spectroscopy characterization

[0154] The six benzotriazine diradical compounds prepared in Examples 7-12 were subjected to UV-absorbing spectroscopy, and the data were normalized. The results are as follows: Figure 11 As shown.

[0155] from Figure 11 As can be seen, all six benzotriazine diradical compounds exhibit a strong absorption peak in the ultraviolet wavelength range (600–1000 nm), corresponding to the π→π* transition in the aromatic ring. The maximum absorption wavelength differs due to the influence of substituents.

[0156] The optical band gap E of the six benzotriazine diradical compounds can be calculated based on their initial absorption wavelengths in the ultraviolet absorption spectra. g opt The values ​​are 1.31, 1.35, 1.31, 1.31, 1.31 and 1.31 eV, respectively.

[0157] The above results show that the spectra of the six compounds prepared in this invention conform to the typical optical absorption characteristics of the Blatter diradical, further proving the accuracy of the molecular structure of the obtained products.

[0158] (2) Infrared spectroscopy characterization

[0159] The six benzotriazine diradical compounds prepared in this invention were characterized by infrared spectroscopy, and the results are as follows: Figure 12 As shown in the figure. It can be seen from the figure that in the wavenumber range of 3300–3500 cm⁻¹... -1Within the range, no typical NH stretching vibration absorption peak was observed, proving that benzotriazine diradical compounds were successfully synthesized under the oxidation of DBU.

[0160] (II) Cyclic Voltmeter-Ammeter Test

[0161] Cyclic voltammetry tests were performed on the six benzotriazine diradical compounds prepared in this invention: anhydrous dichloromethane was used as solvent, 0.1M Bu4NPF6 was used as supporting electrolyte, Ag / AgCl was used as reference electrode, glassy carbon was used as working electrode, platinum wire was used as auxiliary electrode, and the scan rate was 100mV / s.

[0162] Cyclic voltammetry diagrams of the six compounds are shown below. Figure 13 As shown, the measured value of ferrocene is 0.49 eV. The energy levels of HOMO and LUMO are calculated using the following formula:

[0163]

[0164] Figure 13 This invention reveals that the six benzotriazine diradical compounds prepared in this invention all exhibit reversible redox behavior. Calculations based on the formula show that the HOMO energy levels of the six compounds are -4.51, -4.49, -4.50, -4.53, -4.65, and -4.66 eV; the LUMO energy levels are -3.43, -3.44, -3.45, -3.46, -3.47, and -3.44 eV; and their band gaps are 1.08, 1.05, 1.05, 1.07, 1.18, and 1.22 eV, respectively. For organic semiconductors, a smaller band gap makes it easier for electrons to be excited from the valence band to the conduction band, resulting in a higher intrinsic carrier concentration and higher conductivity. Therefore, the six benzotriazine diradical compounds prepared in this invention can be applied in electronic devices.

[0165] (III) Thermogravimetric Analysis (TGA)

[0166] The thermal properties of the NCN-D, NNO2-D, NEt-D, NMeO-D, NPeO-D, and NDeO-D benzotriazine diradical compounds prepared in this invention were tested by thermogravimetric analysis (TGA) under a nitrogen atmosphere. The results are as follows: Figure 14 As shown, all compounds exhibit good thermal stability, with thermal decomposition temperatures (5% weight loss temperatures) of 260℃, 334℃, 316℃, 342℃, 317℃, and 319℃, respectively. This indicates that the benzotriazine diradical compounds prepared in this invention can withstand thermal degradation in storage devices and near-infrared detectors, and have a wide range of applications in practical applications.

[0167] (iv) Photothermal performance testing

[0168] At room temperature, different optical power densities (0.2–1.0 W·cm⁻¹) were used. -2 The solid molecular surfaces of the six benzotriazine diradical compounds prepared in this invention were irradiated with an 808 nm laser, and their photothermal properties were tested. The results are as follows: Figure 15 As shown. All molecules possess highly efficient photothermal conversion capabilities. Furthermore, by exposing the synthesized diradical molecules to a laser (1.0 W·cm⁻¹), -2 Their photostability was tested by subjecting them to 10 cycles of heating and cooling under irradiation, and the results are as follows: Figure 15 As shown, the six benzotriazine diradical compounds exhibited good photostability after 10 cycles with increasing temperature. Therefore, the six benzotriazine diradical compounds prepared in this invention can demonstrate good performance in near-infrared detectors and temperature-controlled films.

[0169] (v) Magnetic characterization (ESR characterization)

[0170] One mg of each of the six benzotriazine diradical compounds prepared in this invention was added to dichloromethane to prepare a 0.001 M solution. The ESR signals of the resulting solutions and solids were measured respectively, and the results are as follows: Figure 16 As shown in the figure, the six benzotriazine diradical compounds prepared in this invention are all magnetic at room temperature, and the magnetic properties of their thin films decrease with decreasing temperature, while the spectral linewidths gradually narrow with increasing temperature.

[0171] Example 14: Fabrication of a near-infrared detector

[0172] This embodiment fabricates a near-infrared detector. The device comprises two parts: a support group and a response group, as shown in the schematic diagram below. Figure 17 As shown, the support assembly is formed by bonding a cover glass slide and PDMS, and the response assembly is prepared by uniformly dispersing any one of the benzotriazine diradical compounds in an ionic liquid.

[0173] The fabrication steps of the near-infrared detector are as follows:

[0174] S1: Preparation of the support assembly

[0175] A mixture of prepolymer (Sylgard 184Silicone Elastomer Base, Dow Corning, USA) and curing agent (Sylgard 184Silicone Elastomer Curing Agent, Dow Corning, USA) at a mass ratio of 10:1 was prepared. The thoroughly mixed mixture was cast into a 2 mm thick ring-containing mold. After curing in a drying oven at 80°C for 4 hours, a PDMS ring (inner and outer diameters: 0.6 cm and 1 mm) was obtained by peeling it from the mold. After plasma treatment for 60 seconds, an uncured layer of PDMS was applied to both the top and bottom of the PDMS ring under heating conditions. Clean coverslips were then bonded to both the top and bottom of the ring, and the mixture was further dried and cured at 80°C to obtain the support assembly. The center of the ring forms a sealing cavity with a diameter of 0.6 cm.

[0176] S2: Fabrication of Near-Infrared Detectors

[0177] The response group was prepared by injecting ionic liquid and benzotriazine diradical compound into the sealed cavity of the support group through a syringe and then dispersing them uniformly by oscillation. Two copper wire electrodes were then inserted at relative positions on the PDMS ring of the support group, with one end contacting the response group and the other end connected to the external circuit, thus obtaining the near-infrared detector.

[0178] Example 15: Performance Testing of Near-Infrared Detectors

[0179] The response group of the near-infrared detector was irradiated with near-infrared light, and the change in conductivity was measured using an electrochemical workstation connected to a copper wire electrode. The results are as follows: Figure 18The figures show schematic diagrams of the testing process of the near-infrared detector, response value changes of response groups prepared by four benzotriazine diradical compounds (NNO2-D, NET-D, NMeO-D, and NPeO-D) combined with the [OMIm][PF6] ionic liquid in Examples 8-11 under different optical power densities of 808 nm near-infrared light irradiation, and response value changes of response groups prepared by the benzotriazine diradical compound NMeO-D molecule prepared in Example 10 combined with five different types of ionic liquids [EMIm][AC], [OMIm][AC], [BMIm][PF6], [HMIm][PF6], and [OMIm][PF6] under different optical power densities of 808 nm near-infrared light irradiation. Experimental results show that the detector can respond rapidly and generate significant electrical signal changes as the near-infrared laser is turned on and off. We define the response value ΔG / G0 to quantify this change, where G0 represents the initial conductivity and ΔG is the change in conductivity. The tests showed a positive correlation between the response value and the near-infrared light radiation power; that is, the response value increased with increasing light power. By comparing the combined effects of four different benzotriazine diradical compounds (NNO2-D, NEt-D, NMeO-D, and NPeO-D) with the [OMIm][PF6] ionic liquid, and the combined effects of NMeO-D molecules with five different types of ionic liquids ([EMIm][AC], [OMIm][AC], [BMIm][PF6], [HMIm][PF6], and [OMIm][PF6]), we found that the combination of NMeO-D molecules with the [OMIm][PF6] ionic liquid exhibited the best electro-response performance, with a response value as high as 4000% at a specific light power of 808 nm and excellent repeatable switching response characteristics.

[0180] Example 16: Fabrication of Organic Resistive Switching Memory

[0181] This embodiment fabricates an organic resistive switching memory. The device comprises three layers, from bottom to top: a substrate layer, an organic active layer, and a top electrode layer. Its structural schematic diagram is shown below. Figure 19 As shown, the substrate layer is ITO glass, the organic active layer is prepared from any one of benzotriazine diradical compounds, and the top electrode layer is an aluminum electrode deposited using a thermal evaporation apparatus. In memory, the organic active layer is a crucial component. An organic active layer with good charge transport properties allows charges to move rapidly within the active layer during data writing and reading, thereby improving read / write speeds. When a write voltage is applied, the molecules in the active layer undergo oxidation, forming a stable state to represent binary information of "0" or "1".

[0182] The fabrication steps of the storage device are as follows:

[0183] S1: Preparation of the organic active layer

[0184] A benzotriazine diradical compound was prepared into a 2 mg / mL solution using chlorobenzene as the solvent. A 1.5 × 1.5 cm ITO glass and a 2 × 2 cm coverslip (used as a scraper) were sequentially ultrasonically vibrated with dish soap and water, ultrapure water, and isopropanol for 20 min each, and then dried with nitrogen. The cleaned ITO glass was then subjected to plasma treatment for 600 s to make the ITO surface more hydrophilic, facilitating the formation of a crystalline film of the compound solution on the ITO surface.

[0185] Thin films were prepared by coating ITO glass with a solution of a benzotriazine diradical compound using a doctor blade coater, resulting in the active layer of the storage device. The coating conditions were: a 45° angle between the doctor blade and the substrate surface, a doctor blade height of 100 μm from the ITO surface, and a coating speed of 20 μm / s.

[0186] S2: Fabrication of Organic Memory

[0187] The electrode mask and the thin film were attached and placed in the evaporation apparatus. The aluminum electrode deposition thickness was set to 100 nm, and the deposition conditions were as follows: 8 × 10⁻⁶ -4 Under vacuum conditions of Pa, the evaporation rate is The organic resistive switching memory was ultimately obtained.

[0188] Example 17: Performance Testing of Organic Resistive Switching Memory Devices

[0189] (1) Characterization of polarized morphology of active layer

[0190] The polarized morphology of the thin film of the NDeO-D benzotriazine diradical compound molecule prepared in Example 12 is as follows: Figure 20 As shown, the molecules have good crystal orientation.

[0191] (2) GIWAXS characterization of the active layer

[0192] The GIWAXS characterization of the NDeO-D benzotriazine diradical compound molecules prepared in Example 12 is as follows: Figure 21 As shown, clear, sharp, and distinct spots were observed, indicating that molecules can form a well-defined crystalline film.

[0193] (3) IV Characteristic Experiment

[0194] The device was tested using a Keithley 4200A-CVIVMULTI-SWITCH. A closed-loop scan was performed from -4V to 4V. Starting at 0V, the voltage was gradually increased to 4V in 10mV steps, then gradually decreased to -4V in the same steps, and then increased back to 0V in the same steps. Current values ​​were recorded during this period to depict the IV characteristics.

[0195] like Figure 22 The image shows the IV characteristic curves of an organic resistive switching memory sample prepared using the NDeO-D benzotriazine diradical compound molecule prepared in Example 12. It can be seen that the compound exhibits WORM-type multi-stage storage performance, with a threshold voltage of 2.9V and an on / off ratio of 10. 5 This indicates that it can be written to once and read from multiple times, storing multiple different states in the storage medium.

[0196] Example 18: Preparation of an Energy-Saving House

[0197] This embodiment prepares an energy-saving house for thermal management. The device includes two parts: a temperature-controlling film and a glass support plate, as shown in the schematic diagram below. Figure 23 As shown, the temperature-controlling film is prepared by uniformly dispersing any one of the benzotriazine diradical compounds in PU, followed by molding and solvent evaporation. When the photothermal temperature-controlling film absorbs light energy, the photon energy absorbed by the film containing the benzotriazine diradical compound is converted into heat energy, raising the temperature of the film surface and reducing the heat conduction effect into the room, thereby achieving the purpose of cooling and energy saving of the building.

[0198] The preparation steps for an energy-saving house are as follows:

[0199] S1: Preparation of temperature-controlled film

[0200] PU was dissolved in N,N-dimethylformamide (DMF) solution by heating in a 60°C water bath. A benzotriazine diradical compound was then added, and after complete mixing, the mixture was poured onto a clean glass plate and heated at 60°C for 24 hours. After the DMF evaporated completely, a PU film containing the mixed benzotriazine diradical compound was obtained, which is the temperature-controlled film.

[0201] S2: Preparation of Energy-Saving Houses

[0202] Cut the temperature control film to the appropriate size and attach it to the commercially available glass support plate. The other five sides are wrapped with insulation material.

[0203] Example 19: Performance Testing of an Energy-Saving House

[0204] The transmittance of the energy-saving roof temperature control film prepared using the NMeO-D benzotriazine diradical compound molecule prepared in Example 10 was tested using a UV-Vis spectrophotometer. The transmittance was measured using a conventional PU temperature control film (without the benzotriazine diradical compound prepared in this invention), a PU film with a mass concentration of 0.1% wt%, a PU film with a mass concentration of 0.3% wt%, and a PU film with a mass concentration of 0.5% wt%. The results are as follows: Figure 24 As shown, the temperature-controlled film can effectively resist the intrusion of ultraviolet light and has good transmittance to other light. With the increase of the mass concentration of NMeO-D benzotriazine diradical compounds, the effect of resisting ultraviolet light is enhanced.

[0205] An energy-saving house was irradiated using a solar simulator emitting one beam of sunlight. Temperature changes inside the house, prepared using NMeO-D benzotriazine diradical compounds (prepared in Example 10), were recorded using a thermometer. Temperature changes were tested under three conditions: using a PU temperature-controlled film, a PU + 0.3% wt% NMeO-D temperature-controlled film, and a PU + 0.5% wt% NMeO-D temperature-controlled film. The results are as follows: Figure 25 As shown. The results show that when using PU + 0.3% wt NMeO-D temperature-controlling film, the indoor temperature of the energy-saving house with the film applied can decrease by 1°C within one hour; when using PU + 0.5% wt NMeO-D temperature-controlling film, the indoor temperature of the energy-saving house with the film applied can decrease by 2°C within one hour. When the energy-saving house prepared using the NMeO-D benzotriazine diradical compound molecule prepared in Example 10 is placed in a natural environment, the temperature change inside the energy-saving house is as follows. Figure 26 As shown, when using PU + 0.5%wt NMeO-D temperature control film, after a day of sunlight exposure, the indoor temperature of the energy-saving house is about 6°C lower than that of the glass room without the temperature control film, effectively achieving the goal of energy saving and environmental protection.

[0206] In summary, the benzotriazine diradical organic magnetic compounds prepared in this invention possess excellent magnetic properties, thermal stability, superior photothermal conversion capabilities, reversible redox properties, and film-forming ability, making them suitable for applications in thermal management, near-infrared detectors, and memory devices. This demonstrates the promising application prospects of benzotriazine diradical molecules in photothermal and memory device fields.

Claims

1. A benzotriazine diradical compound characterized in that, The structural formula is shown as Formula 1: wherein R is selected from cyano, nitro, -0-(CH2) n CH3or -CH2CH3, wherein n is 0, 4, 9.

2. Process for the preparation of the benzotriazine diradical compounds according to claim 1, characterized in that, The method comprises the following steps: S1: Compound A and compound B are mixed uniformly in tetrahydrofuran, then triethylamine is added, and the mixture is heated to reflux at 85-90°C for 24-48 hours to obtain an intermediate product; S2: The intermediate product obtained in step S1 is dissolved in dichloromethane, then ethanol is added, air is introduced, and 1,8-diazabicyclo[5.4.0]undec-7-ene is added to bubble and stir to react, after the reaction is completed, the mixture is filtered, the filter cake is washed with ethyl acetate, and then the benzotriazine biradical compound shown as Formula 1 is obtained; The structural formula of the compound A is selected from any one of Formulae a-1, a-2, a-3, a-4, a-5 and a-6: The structural formula of the compound B is shown as Formula b:

3. The preparation method according to claim 2, characterized in that, In step S1, the molar ratio of compound A to compound B is (2-3):1, and the molar ratio of triethylamine to compound A is (1-3):1; in step S2, the molar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene to compound A is 1:(1-2).

4. The production method according to claim 3, characterized by, After the reaction in step S1 is completed, the reaction solution is cooled to room temperature, filtered, and the filtrate is collected; the filtrate is subjected to rotary evaporation under reduced pressure to remove the solvent, and the intermediate product is obtained.

5. The preparation method according to claim 2, characterized in that, The compound A is prepared by the following method: Compound C and triphenylphosphine are added to acetonitrile, then carbon tetrachloride is added, and the mixture is stirred at room temperature to react; after the reaction is completed, the mixture is filtered, and the filtrate is separated and purified to obtain compound A; wherein the structural formula of the compound C is selected from any one of Formulae c-1, c-2, c-3, c-4, c-5 and c-6: The molar ratio of the compound C to triphenylphosphine is 1:(1-2), and the molar ratio of the carbon tetrachloride to the compound C is (1-2):

1.

6. The preparation method according to claim 5, characterized in that, The compound C is obtained by amidation reaction of compound D and compound E; wherein the structural formula of the compound D is selected from any one of Formulae d-1, d-2, d-3, d-4, d-5 and d-6, and the structural formula of the compound E is shown as Formula e:

7. Use of the benzotriazine biradical compound in claim 1 in the preparation of an organic resistive random access memory, a near-infrared detector and a temperature-controllable film.

8. Use according to claim 7, characterized in that, The organic resistive random access memory comprises a substrate layer, an organic active layer and a top electrode layer, and the organic active layer is prepared from any one of the benzotriazine biradical compounds in claim 1.

9. Use according to claim 7, characterized in that, The near-infrared detector comprises a support group and a response group, and the response group is prepared by uniformly dispersing any one of the benzotriazine biradical compounds in claim 1 in an ionic liquid.

10. Use according to claim 7, characterized in that, The temperature-controllable film is a thin film prepared by adding the benzotriazine biradical compound to necessary film-forming materials.

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