Benzotriazine diradical compound, preparation method and application of benzotriazine diradical compound in organic resistive random access memory, near-infrared detector and temperature control film

Abstract

The invention belongs to the technical field of new materials, and particularly relates to a benzotriazine diradical compound, a preparation method and application of the benzotriazine diradical compound in an organic resistive random access memory, a near-infrared detector and a temperature control film. The benzotriazine biradical organic magnetic compound prepared by the invention has good magnetism and reversible oxidation-reduction characteristic and film-forming property, and can be applied to an organic resistive random access memory; in addition, the material has good thermal stability and excellent photothermal conversion capability, and can be applied to near-infrared detectors and temperature control films. The prepared organic resistive random access memory has good storage performance; the prepared near-infrared detector has ultrahigh electric response efficiency; the prepared temperature control film has good temperature control and energy saving effects.

Description

Technical Field

[0001] The present invention belongs to the technical field of new materials, and in particular relates to a benzotriazine diradical compound, a preparation method and applications of the compound in organic resistive random access memory, a near-infrared detector and a temperature control film. Background Art

[0002] Biradical molecules are an important cross-cutting direction in many fields such as synthetic chemistry, functional materials, and nanotechnology. Delocalized biradicals can be divided into quinone and non-quinone structures. Generally, molecules with two radicals in a para-position are quinone structures, and their spin directions are opposite. Quinone molecules are widely studied because of their low band gap energy, bipolar characteristics, long-wave absorption, convertible spin states, and conductor properties. Compared with other types of free radicals, Blatter radicals have unique electrical and magnetic properties, such as antiferromagnetic or ferromagnetic interactions, spin π delocalization, narrow electrochemical windows, and low excitation energy. They have mature synthetic routes and ultra-high stability. In addition, the unique advantage of Blatter radicals is that their structure is highly modifiable. There are three aromatic sites that can regulate molecular properties. However, the current molecular structure based on Blatter radicals has problems such as weak absorption capacity in various light bands, limited detection range in the near-infrared region, photothermal performance needs to be further improved, unsystematic application research, gaps in research in the field of electronic devices, and high potential value that has not been developed. Therefore, it is crucial to design and synthesize several molecules, introduce double Blatter radicals to narrow the band gap of organic conjugated molecules to improve photothermal conversion efficiency, obtain high absorption in the near-infrared region, and make breakthroughs in the storage field based on single radicals. Summary of the invention

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

[0004] To achieve the purpose of the invention, the technical solution adopted by the present invention is as follows:

[0005] The first aspect of the present 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, -O-(CH2) n Any one of CH3 or -CH2CH3, wherein n is 0, 4, or 9.

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

[0009] S1: Compound A and compound B are added to tetrahydrofuran and mixed evenly, and then triethylamine is added, and the mixture is heated under reflux at 85°C to 90°C for 24h to 48h to separate the intermediate product;

[0010] S2: dissolving the intermediate product obtained in step S1 in a small amount of dichloromethane, adding a large amount of ethanol, introducing air, and adding 1,8-diazabicyclo[5.4.0]undec-7-ene at the same time, bubbling and stirring to react, filtering after the reaction is completed, washing and purifying the filter cake with ethyl acetate to obtain a benzotriazine diradical compound as shown in Formula 1;

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

[0012]

[0013] The structural formula of the 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; 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 filtrate is subjected to reduced pressure rotary evaporation to remove the solvent to obtain an intermediate product.

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

[0018] Compound C and triphenylphosphine are added to acetonitrile, and then carbon tetrachloride is added, and the mixture is stirred at room temperature for reaction; 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 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] The compound C is obtained by amidation reaction of compound D and compound E. The specific preparation method is: adding compound E and triethylamine to tetrahydrofuran, stirring for 10min to 15min in an ice-water bath, and then adding compound D to obtain a mixed solution; naturally warming to room temperature, stirring and reacting for 18 to 24h, filtering after the reaction, collecting the filtrate, and evaporating the solvent to obtain a solid product, and purifying the solid product to obtain compound C; wherein the structural formula of the 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 the present invention provides the use of the benzotriazine diradical compound described in the first aspect in the preparation of an organic resistive random access memory, a near-infrared detector, and a temperature control film.

[0025] 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 diradical compounds described in the first aspect.

[0026] The near-infrared detector comprises 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 in an ionic liquid;

[0027] The temperature control film is a film prepared by adding the benzotriazine diradical compound to a necessary film-forming material. The film-forming material is preferably PU. Further, multiple support plates are enclosed to form a side wall, and the top is covered with the temperature control film added with the benzotriazine diradical compound, which can be made into an energy-saving house and further applied to thermal management.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The present invention successfully prepared benzotriazine diradical compounds, and reduced the band gap of organic conjugated molecules by introducing di-Blatter radicals. The ground state structure is jointly contributed by the closed-shell quinone form and the open-shell diradical, giving the material a certain degree of diradical properties. The benzotriazine diradical organic magnetic compounds prepared by the present invention have good magnetic properties, reversible redox properties and film-forming properties, and can be used in organic resistive random access memory; in addition, they have good thermal stability and excellent light-to-heat conversion capabilities, and can be used in near-infrared detectors and temperature control films.

[0030] 2. The preparation method of the benzotriazine diradical compound provided by the present invention is simple, reduces time cost, and the raw materials are cheap and easily available, which provides a method for the preparation of diradicals.

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

[0032] 4. The near-infrared detector based on benzotriazine diradical compounds provided by the present 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 the present invention has good temperature control and energy-saving effects and has extremely high application value in the field of energy and environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The compound A of the structural formula a-3 is 1 HNMR spectra;

[0035] Figure 2 The compound C of the structural formula shown in formula c-3 1 HNMR spectra;

[0036] Figure 3 The compound A of the structural formula a-5 is 1 HNMR spectra;

[0037] Figure 4 The compound C of the structural formula shown in formula c-5 1 HNMR spectra;

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

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

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

[0041] Figure 8 is a mass spectrum of a benzotriazine diradical compound having a structural formula as shown in Formula 10;

[0042] Fig. 9 is a mass spectrum of a benzotriazine diradical compound having a structural formula as shown in Formula 11;

[0043] Fig.10 is a mass spectrum of a benzotriazine diradical compound having a structural formula as shown in Formula 12;

[0044] Fig.11The UV spectra of five benzotriazine diradical compounds prepared in Examples 7 to 12;

[0045] Fig.12 The infrared spectra of five benzotriazine diradical compounds prepared in Examples 7 to 12;

[0046] Fig.13 Cyclic voltammograms of five benzotriazine diradical compounds prepared in Examples 7 to 12;

[0047] Fig.14 Thermogravimetric analysis diagrams of benzotriazine diradical compounds prepared in Examples 7 to 12;

[0048] Fig.15 The photothermal performance diagram of the benzotriazine diradical compounds prepared in Examples 7 to 12;

[0049] Fig.16 The ESR graphs of the benzotriazine diradical compounds prepared in Examples 7 to 12;

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

[0051] Fig.18 The test process and electrical response performance diagram of the near infrared detector prepared in Example 14;

[0052] Fig.19 A structural diagram of an organic resistive random access memory prepared in Example 16;

[0053] Fig. 20 This is a polarized morphology image of a thin film of a benzotriazine diradical compound prepared in Example 12;

[0054] Fig.21 This is the GIWAXS characterization diagram of the benzotriazine diradical compound prepared in Example 12;

[0055] Fig. 22 This is a graph showing IV characteristics of the organic resistive random access memory prepared in Example 16;

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

[0057] Fig.24 This is a light transmittance diagram of the temperature-control film for an energy-saving house prepared in Example 18;

[0058] Fig.25 This is a diagram of the indoor temperature of the energy-saving house prepared in Example 18 under simulated sunlight;

[0059] Fig.26This is a diagram of the indoor temperature of the energy-saving house prepared in Example 18 under natural light in one day. DETAILED DESCRIPTION

[0060] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0061] Example 1

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

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

[0064] (2) After the reaction is completed, if any product is precipitated, the bottle is first washed with cold acetonitrile solution, the product is filtered and collected, and the filtrate is purified by silica gel column chromatography using petroleum ether as an eluent. The eluate is collected and the solvent is removed by evaporation under reduced pressure. The obtained product is combined with the filtered product to obtain compound A.

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

[0066]

[0067] The reaction equation for preparing compound A of formula a-1 is:

[0068]

[0069] Wherein, the preparation method of compound C having the structural formula shown in formula c-1 is:

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

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

[0072]

[0073] The reaction equation for preparing compound C with the structural formula shown in formula c-1 is:

[0074]

[0075] Example 2

[0076] A compound A having a structural formula as shown in formula a-2, the substance name is 4-Nitro-N-phenylbenzenecarbohydrazonoyl chloride, and the CAS number is 20147-55-1:

[0077]

[0078] The preparation method of the compound A with the structural formula shown in formula a-2 described in this embodiment is basically the same as the preparation method of the compound A with the structural formula shown in formula a-1 in Example 1, except that: the structural formula of the 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 with the structural formula shown in formula c-2 is basically the same as the preparation method of compound C in Example 1, except 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 a structural formula as shown in formula a-3, the substance name is Benzenecarbohydrazonoylchloride, 4-ethyl-N-phenyl-, [C(Z)]-, and the CAS number is 3058697-47-2:

[0084]

[0085] The preparation method of the compound A with the structural formula shown in formula a-3 described in this embodiment is basically the same as the preparation method of the compound A with the structural formula shown in formula a-1 in Example 1, except that: the structural formula of the 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 with the structural formula shown in formula c-3 is basically the same as the preparation method of compound C in Example 1, except 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] The prepared compound A was subjected to NMR analysis (NMR results are shown in Figure 1 as shown): 1 H NMR (400MHz, Chloroform-d) δ8.00 (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, 1.2 Hz, 1H), 2.69 (q, J=7.6 Hz, 2H), 1.26 (t, J=7.6 Hz, 3H). The above results confirmed that the obtained product was the target product.

[0090] The prepared compound C was subjected to NMR analysis (the NMR results are shown in Figure 2 as shown): 1 H NMR (400 MHz, 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, 1.1 Hz, 3H), 2.71 (q, J=7.6 Hz, 2H), 1.26 (t, J=7.6 Hz, 3H). The above results confirmed that the obtained product was the target product.

[0091] Example 4

[0092] A compound A with a structural formula as shown in formula a-4, the substance name is 4-Methoxy-N-phenylbenzenecarbohydrazonoyl chloride, and the CAS number is 40277-63-2:

[0093]

[0094] The preparation method of the compound A of the structural formula a-4 described in this embodiment is basically the same as the preparation method of the compound A of the structural formula a-1 described in Example 1, except that: the structural formula of the 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 with the structural formula shown in formula c-4 is basically the same as the preparation method of compound C in Example 1, except 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 having a structural formula as shown in formula a-5:

[0100]

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

[0102]

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

[0104]

[0105] The prepared compound A was subjected to NMR analysis (NMR results are shown in Figure 3 as shown): 1 H NMR (400MHz, Chloroform-d) δ7.93 (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). The above results confirmed that the obtained product was the target product.

[0106] The prepared compound C was subjected to NMR analysis (the NMR results are shown in Figure 4 as shown): 1 H NMR (400MHz, Chloroform-d) δ8.16 (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). The above results confirmed that the obtained product was the target product.

[0107] Example 6

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

[0109]

[0110] The preparation method of the compound A of the structural formula a-6 described in this embodiment is basically the same as the preparation method of the compound A of the structural formula a-1 described in Example 1, except that: the structural formula of the 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 with the structural formula shown in formula c-6 is basically the same as the preparation method of compound C in Example 1, except 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 preparation method of the above-mentioned benzotriazine diradical compound comprises the following specific steps:

[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, and the filtrate was collected and evaporated under reduced pressure to remove the solvent to obtain an intermediate product.

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

[0120]

[0121] S2: The intermediate product (1 eq) was dissolved in anhydrous dichloromethane (20 mL) and a large amount of ethanol (120 mL) was added. 1,8-diazabicyclo[5.4.0]undec-7-ene (2 eq) was added, air was introduced, and the reaction was stirred by bubbling. After the reaction was completed, the mixture was filtered and the filter cake was washed and purified with ethyl acetate to obtain the target product compound.

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

[0123]

[0124] The benzotriazine diradical compound prepared in this example was subjected to mass spectrometry analysis. The results are as follows: Figure 5 As shown, mass spectrometry analysis HRMS (ESI+): [MH]+C 38 H 22 N8 2Calculated 590.3685, found 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 compounds 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 prepared in Example 2 with the structural formula shown in formula a-2 (the amount of compound A remains unchanged).

[0129] The benzotriazine diradical compound prepared in this example was subjected to mass spectrometry analysis. The results are as follows: Figure 6 As shown, mass spectrometry analysis HRMS (ESI+): [MH]+C 36 H 22 N8O4 2 Calculated 630.1764, found 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 Formula 1-3:

[0132]

[0133] The preparation method of the benzotriazine free radical compounds 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 prepared in Example 3 with the structural formula shown in formula a-3 (the amount of compound A remains unchanged).

[0134] The benzotriazine diradical compound prepared in this example was subjected to mass spectrometry analysis. The results are as follows: Figure 7 As shown, mass spectrometry analysis HRMS (ESI+): [MH]+C 40 H 32 N6 2 Calculated 596.2688, found 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 Formula 1-4:

[0137]

[0138] The preparation method of the benzotriazine free radical compounds 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 prepared in Example 4 with the structural formula shown in formula a-4 (the amount of compound A remains unchanged).

[0139] The benzotriazine diradical compound prepared in this example was subjected to mass spectrometry analysis. The results are as follows: Figure 8 As shown, mass spectrometry analysis HRMS (ESI+): [MH]+C 38 H 28 N6O2 2· Calculated 600.2274, found 600.0906. The above results confirm that the obtained product is the target product.

[0140] Embodiment 11

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

[0142]

[0143] The preparation method of the benzotriazine free radical compounds 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 prepared in Example 5 with the structural formula shown in formula a-5 (the amount of compound A remains unchanged).

[0144] The benzotriazine diradical compound prepared in this example was subjected to mass spectrometry analysis. The results are as follows: Fig. 9 As shown, mass spectrometry analysis HRMS (ESI+): [MH]+C 46 H 44 N6O2 2· Calculated 712.3529, found 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 Formula 1-6:

[0147]

[0148] The preparation method of the benzotriazine free radical compounds 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 prepared in Example 6 with the structural formula shown in formula a-6 (the amount of compound A remains unchanged).

[0149] The benzotriazine diradical compound prepared in this example was subjected to mass spectrometry analysis. The results are as follows: Fig.10 As shown, mass spectrometry analysis HRMS (ESI+): [MH]+C 56 H 64 N6O2 2· Calculated 852.5091, found 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 to 12 were named NCN-D, NNO2-D, NEt-D, NMeO-D, NPeO-D, and NDeO-D, respectively, and their performance characterization was tested.

[0152] (I) Optical characterization

[0153] (1) UV-absorption spectroscopy characterization

[0154] The six benzotriazine diradical compounds prepared in Examples 7 to 12 were subjected to UV-absorption spectrum measurement, and the data were normalized. The results are as follows: Fig.11 shown.

[0155] from Fig.11 It can be seen that in the ultraviolet wavelength range (600-1000nm), the six benzotriazine diradical compounds all have a strong absorption peak, corresponding to the π→π* transition in the aromatic ring. Due to the influence of the substituents, the maximum absorption wavelength is different.

[0156] According to the initial absorption wavelengths of the six benzotriazine diradical compounds in the ultraviolet absorption spectrum, the optical band gaps E of the six compounds can be calculated. g opt They are 1.31, 1.35, 1.31, 1.31, 1.31 and 1.31 eV respectively.

[0157] The above results show that the spectra obtained from the six compounds prepared in the present invention are consistent with the typical optical absorption characteristics of the Blatter diradical, further proving the accuracy of the molecular structures of the obtained products.

[0158] (2) Infrared spectroscopy characterization

[0159] The six benzotriazine diradical compounds prepared by the present invention were characterized by infrared spectroscopy. Fig.12 As shown in the figure, at wave numbers 3300-3500cm -1In the range of , 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 voltammetry test

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

[0162] The cyclic voltammograms of the six compounds are shown in Fig.13 As shown, the measured ferrocene is 0.49 eV. The HOMO and LUMO energy levels are calculated by the following formula:

[0163]

[0164] Fig.13 It is revealed that the six benzotriazine diradical compounds prepared by the present invention all have reversible redox behavior. According to the formula, the HOMO energy levels of the six compounds are -4.51, -4.49, -4.50, -4.53, -4.65 and -4.66 eV respectively; the LUMO energy levels are -3.43, -3.44, -3.45, -3.46, -3.47 and -3.44 eV respectively; and the energy gap differences are 1.08, 1.05, 1.05, 1.07, 1.18 and 1.22 eV respectively. For organic semiconductors, the smaller the band gap, the easier it is for electrons to be excited from the valence band to the conduction band, the higher the intrinsic carrier concentration, and the higher the conductivity. Therefore, the six benzotriazine diradical compounds prepared by the present invention can be used 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 by the present invention were tested by thermogravimetric analysis (TGA) under nitrogen atmosphere. The results are as follows: Fig.14 All compounds showed good thermal stability, and the thermal decomposition temperatures (5% weight loss temperature) were 260°C, 334°C, 316°C, 342°C, 317°C, and 319°C, respectively. This shows that the benzotriazine diradical compounds prepared by the present invention can withstand thermal deterioration in storage devices and near-infrared detectors, and have a wide range of applications in practical applications.

[0167] (IV) Photothermal performance test

[0168] At room temperature, different optical power densities (0.2-1.0 W cm -2 ) irradiated the solid molecular surfaces of the six benzotriazine diradical compounds prepared by the present invention with an 808 nm laser to test their photothermal properties. The results are as follows Fig.15 All molecules have efficient photothermal conversion ability. In addition, by exposing the synthesized diradical molecules to laser light (1.0 W cm -2 ) were used to test their photostability during 10 cycles of heating and cooling. Fig.15 As shown, the six benzotriazine diradical compounds have no change in temperature after 10 cycles, and have good photostability. Therefore, the six benzotriazine diradical compounds prepared by the present invention can show good effects in near-infrared detectors and temperature control films.

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

[0170] 1 mg of the six benzotriazine diradical compounds prepared by the present invention was taken and dichloromethane was added to prepare a solution with a concentration of 0.001 M. The ESR signals of the obtained solution and solid were tested respectively. The results are as follows: Fig.16 As shown in the figure, it can be seen that the six benzotriazine diradical compounds prepared by the present invention are all magnetic at room temperature, and the magnetic properties of their films decrease as the temperature decreases, while the spectral line width gradually narrows as the temperature increases.

[0171] Example 14: Preparation of near-infrared detector

[0172] This embodiment prepares a near-infrared detector, which includes two parts, namely a support group and a response group. The schematic diagram of its structure is shown in FIG. Fig.17 As shown, the support group is formed by bonding a cover glass and PDMS, and the response group is prepared by uniformly dispersing any one of benzotriazine diradical compounds in an ionic liquid.

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

[0174] S1: Preparation of support group

[0175] A mixture of prepolymer (Sylgard 184Silicone Elastome Base, Dow Corning, USA) and curing agent (Sylgard 184Silicone Elastomer Curing Agent, Dow Corning, USA) was prepared at a mass ratio of 10:1, and the thoroughly mixed mixture was cast into a ring-containing mold with a thickness of 2 mm. After curing in a drying oven at 80°C for 4 hours, a PDMS (inner and outer diameters: 0.6 cm and 1 mm) ring was obtained by peeling from the mold. After plasma treatment for 60 seconds, a layer of uncured PDMS was applied to the upper and lower parts of the PDMS ring under heating conditions, and a clean cover glass was bonded to the upper and lower parts, and continued to dry and cure at 80°C to obtain a support group. The center of the ring is a sealed cavity with a diameter of 0.6 cm.

[0176] S2: Preparation of near-infrared detectors

[0177] The response group is prepared by injecting ionic liquid and benzotriazine diradical compounds into the sealed cavity of the support group through a needle tube and evenly dispersing them by oscillation. Then two copper wire electrodes are inserted at relative positions on the PDMS ring of the support group, one end of which contacts the response group and the other end is connected to the external circuit to obtain a near-infrared detector.

[0178] Example 15: Performance test of near infrared detector

[0179] The response group of the near-infrared detector was irradiated with near-infrared light, and the change of conductivity was measured by connecting the copper wire electrode with an electrochemical workstation. The results are as follows: Fig.18. The figure shows the schematic diagram of the test process of the near-infrared detector, the response value change diagram of the response group prepared by combining the four benzotriazine diradical compounds NNO2-D, NEt-D, NMeO-D, and NPeO-D prepared in Examples 8 to 11 with the ionic liquid [OMIm][PF6] under the irradiation of near-infrared light of different optical power densities of 808nm, and the response value change diagram of the response group prepared by combining the benzotriazine diradical compound NMeO-D molecule prepared in Example 10 with five different types of ionic liquids [EMIm][AC], [OMIm][AC], [BMIm][PF6], [HMIm][PF6], and [OMIm][PF6] under the irradiation of near-infrared light of different optical power densities of 808nm. The experimental results show that as the near-infrared laser is turned on and off, the detector can respond quickly and produce obvious changes in electrical signals. 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 test shows that the response value is positively correlated with the near-infrared light radiation power, that is, the response value increases as the light power increases. By comparing the combination effect of four different benzotriazine diradical compounds NNO2-D, NEt-D, NMeO-D, and NPeO-D with [OMIm][PF6] ionic liquid, and the combination effect 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 and [OMIm][PF6] ionic liquids showed the best electrical response performance, with a response value of up to 4000% at a specific light power of 808nm and excellent repeatable switching response characteristics.

[0180] Example 16: Preparation of organic resistive random access memory

[0181] In this embodiment, an organic resistive random access memory is prepared. The device includes three layers, which are a substrate layer, an organic active layer and a top electrode layer from bottom to top. The schematic diagram of the structure is shown in FIG. Fig.19 As shown, the substrate layer is ITO glass, the organic active layer is made of any one of the benzotriazine diradical compounds, and the top electrode layer is an aluminum electrode evaporated by a thermal evaporator. In the memory, the organic active layer is a key part. The organic active layer has good charge transfer performance, and its charge can move quickly in the active layer when writing and reading data, thereby improving the read and write speed. When the write voltage is applied, the molecules in the active layer will oxidize to form a stable state to represent the binary information of "0" or "1".

[0182] The steps for preparing the memory device are as follows:

[0183] S1: Preparation of organic active layer

[0184] The benzotriazine diradical compound was prepared into a solution with a concentration of 2 mg / mL, and the solvent used was chlorobenzene. The ITO glass with a size of 1.5×1.5 cm and the cover glass with a size of 2×2 cm (as a scraper) were ultrasonically vibrated for 20 minutes using detergent water, ultrapure water, and isopropanol in turn, and blown dry with N2. The clean ITO glass was treated with plasma for 600 seconds to make the ITO surface more lyophilic, which facilitated the compound solution to form a crystal film on the ITO surface.

[0185] The ITO glass and the prepared benzotriazine diradical compound solution were coated with a scraper to prepare a thin film, thereby obtaining a thin film, i.e., an active layer of a memory device. The scraper coating conditions were as follows: the angle between the scraper and the substrate surface was 45°, the scraper was 100 μm above the ITO surface, and the scraper coating speed was 20 μm / s.

[0186] S2: Preparation of organic memory

[0187] Paste the electrode mask and the film and put them into the evaporation apparatus. Set the aluminum electrode evaporation thickness to 100nm. The evaporation conditions are as follows: -4 Under the vacuum condition of Pa, the evaporation rate is Finally, an organic resistive random access memory is obtained.

[0188] Example 17: Performance test of organic resistive memory device

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

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

[0191] (2) GIWAXS characterization of active layer

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

[0193] (3) IV characteristics test

[0194] The device performance was tested using Keithley 4200A-CVIVMULTI-SWITCH. The scan range was a closed loop scan between -4V and 4V. Starting from 0V, the step size was 10mV and gradually increased to 4V, then gradually decreased to -4V with the same step size, and then increased to 0V with the same step size, and the current value during this period was recorded to depict the IV characteristics.

[0195] like Fig. 22 The IV characteristic curve of the organic resistive random access memory sample prepared by using the NDeO-D benzotriazine diradical compound molecule prepared in Example 12 is shown. It can be seen that the electrical storage behavior of the compound exhibits WORM-type multi-level storage performance, with a threshold voltage of 2.9V and a switching ratio of 10 5 . This means that it can be written once and read multiple times, storing multiple different states in the storage medium.

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

[0197] This embodiment prepares an energy-saving house for thermal management. The device includes two parts, namely a temperature control film and a glass support plate. The schematic diagram of the structure is shown in FIG. Fig.23 As shown, the temperature control film is made by uniformly dispersing any one of the benzotriazine diradical compounds in PU, and is prepared by mold shaping and solvent evaporation. When the photothermal temperature control film absorbs light energy, the temperature control film containing the benzotriazine diradical compound will convert the absorbed photon energy into heat energy, increase the temperature of the film surface, and reduce the temperature conduction effect to the room, thereby achieving the purpose of cooling and energy saving of the building.

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

[0199] S1: Preparation of temperature control film

[0200] The PU was dissolved in a N,N-dimethylformamide (DMF) solution by heating in a 60°C water bath, and a benzotriazine diradical compound was added thereto. After complete blending, the mixture was poured onto a clean glass plate and heated on a 60°C hot plate for 24 hours. After the DMF was evaporated, a PU film mixed with a benzotriazine diradical compound was obtained, i.e., a temperature-controlled film.

[0201] S2: Preparation of Energy-saving House

[0202] The temperature control film is cut into a suitable size and attached to a commercially available glass support plate, and the other five surfaces are wrapped with insulation materials.

[0203] Example 19: Performance test of energy-saving house

[0204] The transmittance of the energy-saving house temperature control film prepared by the NMeO-D benzotriazine diradical compound molecule prepared in Example 10 was tested by ultraviolet-visible spectrophotometer, and the transmittance of the temperature control film under the conditions of ordinary PU temperature control film (without the addition of the benzotriazine diradical compound prepared by the present invention), PU + 0.1%wt NMeO-D temperature control film, PU + 0.3%wt NMeO-D temperature control film and PU + 0.5%wt NMeO-D temperature control film was tested. The results are as follows: Fig.24 As shown, the temperature-control film can effectively resist the invasion 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] A solar simulator emitting 1 sun was used to illuminate the energy-saving house, and the temperature change inside the energy-saving house prepared by the NMeO-D benzotriazine diradical compound molecule prepared in Example 10 was recorded by a thermometer. The temperature change under the PU temperature control film, PU+0.3%wt NMeO-D temperature control film, and PU+0.5%wt NMeO-D temperature control film was tested. The results are as follows Fig.25 The results show that when PU+0.3%wt NMeO-D temperature control film is used, the indoor temperature of the energy-saving house with the temperature control film can drop by 1°C within one hour. When PU+0.5%wt NMeO-D temperature control film is used, the indoor temperature of the energy-saving house with the temperature control film can drop by 2°C within one hour. When the energy-saving house prepared by the NMeO-D benzotriazine diradical compound molecules prepared in Example 10 is placed in a natural environment, the temperature change inside the energy-saving house is as follows: Fig.26 As shown, when PU+0.5%wt NMeO-D temperature control film is used, after a day of sunlight exposure, the maximum internal temperature of the energy-saving house is about 6°C lower than that of the glass house without the temperature control film, effectively achieving the purpose of energy saving and environmental protection.

[0206] In summary, the benzotriazine diradical organic magnetic compound prepared by the present invention has good magnetism, thermal stability, excellent photothermal conversion ability, reversible redox characteristics and film-forming properties, and can be applied to thermal management, near-infrared detectors and memory devices. This confirms the application research prospects of benzotriazine diradical molecules in the field of photothermal and memory devices.

Claims

1. A benzotriazine diradical compound, characterized in that: The structural formula is shown in Formula 1: Wherein, R is selected from cyano, nitro, -O-(CH2) n Any one of CH3 or -CH2CH3, wherein n is 0, 4, or 9.

2. The method for preparing the benzotriazine diradical compound according to claim 1, characterized in that: The following steps are involved: S1: Compound A and compound B are added to tetrahydrofuran and mixed evenly, and then triethylamine is added, and the mixture is heated under reflux at 85°C to 90°C for 24 to 48 hours to separate the intermediate product; S2: dissolving the intermediate product obtained in step S1 in dichloromethane, adding ethanol, introducing air, and adding 1,8-diazabicyclo[5.4.0]undec-7-ene at the same time, bubbling and stirring to react, filtering after the reaction is completed, washing and purifying the filter cake with ethyl acetate to obtain a benzotriazine diradical compound as shown in Formula 1; The structural formula of the compound A is selected from any one of formula a-1, a-2, a-3, a-4, a-5, and a-6: The structural formula of the compound B is shown in formula b:

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

4. The preparation method according to claim 3, characterized in that: 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 reduced pressure rotary evaporation to remove the solvent to obtain an intermediate product.

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, and then carbon tetrachloride is added, and the mixture is stirred at room temperature for reaction; 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 compound C is selected from any one of formulas 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 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:

7. Use of the benzotriazine diradical compound according to claim 1 in the preparation of organic resistive random access memory, near infrared detector and temperature control film.

8. The 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 diradical compounds according to claim 1.

9. The 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 diradical compounds described in claim 1 in an ionic liquid.

10. The use according to claim 7, characterized in that: The temperature control film is a film prepared by adding the benzotriazine diradical compound to necessary film-forming materials.

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