Solid-state charge transfer complex, preparation method and application thereof

Abstract

The application belongs to the technical field of solid-state charge transfer complex, and provides a solid-state charge transfer complex, a preparation method and application thereof, the solid-state charge transfer complex is EtLP6 alpha-TFTN, ethyl skew[6]arene EtLP6 is used as an electron donor, and electron-deficient aromatic four-fluorine p-phenylenedicyanide is used as an electron acceptor. The solid-state charge transfer (CT) complex formed by ethyl skew[6]arene (EtLP6) and electron-deficient aromatic acceptor (four-fluorine p-phenylenedicyanide-TFTN) is constructed in the embodiment of the application, the switch-type gas-induced chromic property of the solid-state charge transfer (CT) complex on 1,3-dioxane and 1,4-dioxane isomer vapor can be used to realize rapid, visualized distinction and detection on 1,3-dioxane and 1,4-dioxane isomer; the solid-state charge transfer complex can be obtained by simple mechanical grinding, and no complex solvent crystallization process is involved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solid-state charge transfer complex, and particularly relates to a solid-state charge transfer complex and a preparation method and application thereof. BACKGROUND

[0002] In many fields such as chemical industry, medicine and pesticide, 1,3-dioxane and 1,4-dioxane are widely used due to their unique performance characteristics. However, in the actual application process, it is difficult to quickly and accurately distinguish and detect them due to their similar physical and chemical properties.

[0003] From the physical properties, the boiling points, melting points and densities of the two compounds are similar, and it is difficult to find obvious differences for effective distinction under conventional physical detection means. In terms of chemical properties, the activities of the two compounds in chemical reactions and the reaction phenomena with various reagents are also similar, making it difficult for traditional chemical analysis methods to work.

[0004] At present, the detection of 1,3-dioxane and 1,4-dioxane mainly relies on gas chromatography, liquid chromatography and other instrument analysis methods. Although gas chromatography has high separation efficiency and sensitivity, the sample needs to be pretreated, including derivatization and other steps, and the operation process is complicated. Liquid chromatography also faces the problem of relatively complex operation, which requires professional technical personnel to operate, and the detection period is long, which cannot meet the demand of rapid detection. In addition, the instrument equipment is expensive, the maintenance cost is high, and a large amount of reagents and consumables are consumed, resulting in high overall detection cost, which to a large extent limits the wide application and frequent detection of 1,3-dioxane and 1,4-dioxane in the actual production process. SUMMARY

[0005] The purpose of the embodiment of the application is to provide a solid-state charge transfer complex, which aims to solve the problems raised in the background art.

[0006] The embodiment of the application is implemented as follows: a solid-state charge transfer complex is EtLP6 alpha-TFTN, which takes ethyl skew[6]arene EtLP6 as an electron donor and electron-deficient aromatic tetracyano-p-phenylenedinitrile as an electron acceptor.

[0007] Another purpose of the embodiment of the application is to provide a preparation method of the solid-state charge transfer complex, which comprises the following steps:

[0008] synthesizing EtLP6;

[0009] preparing solvent-free EtLP6 alpha;

[0010] The EtLP6 alpha and tetrafluoro terephthalonitrile are mixed and then grinded until the color of the mixture changes from white to light yellow, indicating the formation of solid state charge transfer complex, and the molar ratio of the EtLP6 alpha and tetrafluoro terephthalonitrile is 1:1.8-2.2.

[0011] Another purpose of the embodiment of the present application is to provide an application of the solid state charge transfer complex in detecting 1,3-dioxane and 1,4-dioxane.

[0012] The embodiment of the present application can realize rapid, visualized distinction and detection of 1,3-dioxane and 1,4-dioxane isomers by constructing a solid state charge transfer (CT) complex formed by ethyl oblique [6] arene (EtLP6) and electron-deficient aromatic acceptor (tetrafluoro terephthalonitrile-TFTN) and utilizing the switchable gaschromic property of the solid state charge transfer complex to 1,3-dioxane and 1,4-dioxane isomer vapors. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 The preparation flowchart of the solid state charge transfer complex EtLP6 alpha-TFTN provided for the embodiment 1 of the present application is shown in the figure;

[0014] Figure 2 The color change schematic diagram of the gaschromic performance test of the EtLP6 alpha-TFTN provided for the embodiment 2 of the present application is shown in the figure;

[0015] Figure 3 The ultraviolet absorption spectrum of the EtLP6 alpha-TFTN prepared in the embodiment 1 of the present application is shown in the figure;

[0016] Figure 4 The ultraviolet reflection spectrum of the EtLP6 alpha-TFTN prepared in the embodiment 1 of the present application is shown in the figure;

[0017] Figure 5 The PXRD test result of the EtLP6 alpha-TFTN prepared in the embodiment 1 of the present application is shown in the figure;

[0018] Figure 6 The nuclear magnetic resonance hydrogen spectrum result of the EtLP6 alpha-TFTN prepared in the embodiment 1 of the present application under the stimulation of 1,4-dioxane vapor is shown in the figure;

[0019] Figure 7 The nuclear magnetic resonance hydrogen spectrum result of the EtLP6 alpha-TFTN prepared in the embodiment 1 of the present application under the stimulation of 1,3-dioxane vapor is shown in the figure;

[0020] Figure 8UV absorption spectrum of EtLP6a-TFTN prepared in Embodiment 1 of the present application under the vapor stimulation of two dioxane isomers;

[0021] Figure 9 UV reflection spectrum of EtLP6a-TFTN prepared in Embodiment 1 of the present application under the vapor stimulation of two dioxane isomers;

[0022] Figure 10 PXRD test result of EtLP6a-TFTN prepared in Embodiment 1 of the present application under the vapor stimulation of 1,3-dioxane;

[0023] Figure 11 PXRD test result of EtLP6a-TFTN prepared in Embodiment 1 of the present application under the vapor stimulation of 1,4-dioxane;

[0024] Figure 12 Raman spectrum of EtLP6a-TFTN prepared in Embodiment 1 of the present application under the vapor stimulation of two dioxane isomers;

[0025] Figure 13 Top view, side view and two-dimensional packing diagram of the crystal of EtLP6@1,3-dioxane provided in the present application;

[0026] Figure 14 Top view, side view and two-dimensional packing diagram of the crystal of EtLP6@1,4-dioxane provided in the present application;

[0027] Figure 15 Top view, side view and two-dimensional packing diagram of the crystal of EtLP6@TFTN provided in the present application. DETAILED DESCRIPTION

[0028] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below in combination with the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application, and are not used to limit the present application.

[0029] The specific implementation of the present application will be described in detail below in combination with specific embodiments.

[0030] Embodiment 1, a solid-state charge transfer complex EtLP6a-TFTN, the preparation method thereof comprises the following steps:

[0031] 1, synthesis of EtLP6 material, the synthesis path of which is shown as follows:

[0032]

[0033] Into a 500 mL round bottom flask, 3.5 g of 1,4-p-dichlorobenzyl (about 20 mmol) and 13.3 g of p-diethoxybenzene (about 80 mmol) were added and 300 mL of dichloromethane was added to stir at room temperature to completely dissolve, 6.0 g of aluminum chloride (about 45 mmol) was added as a catalyst, after 2 h of reaction at room temperature, stop adding 300 mL of water to quench, after quenching with water, continue to stir for 2 hours, stop stirring, use a 500 mL separatory funnel to separate the lower organic phase, extract three times, then add 5 g of anhydrous sodium sulfate to remove residual water in the organic phase, add 16 g of silica gel powder and ultrasonic it to disperse uniformly, heat in a 35 °C water bath, rotate at 110 rpm, vacuum degree is -12 Pa, remove the solvent by rotary evaporation to obtain the crude product; Add silica gel powder, crude product, anhydrous sodium sulfate, and quartz sand to fill the chromatography column, select a developing agent with a volume ratio of petroleum ether to ethyl acetate of 6:1 to effectively separate the components on the silica gel plate; Use 2000 mL of eluent with a volume ratio of petroleum ether to dichloromethane of 3:1 to elute the remaining p-diethoxybenzene after the reaction is complete; Then, use 2000 mL of eluent with a volume ratio of petroleum ether to dichloromethane of 1:1 to elute the EtLP6 intermediate, and the obtained eluent is rotary evaporated to obtain a white solid, which is dried in a vacuum oven at 80 °C for 12 h to obtain 2.78 g of EtLP6 intermediate (yield about 32%);

[0034] Into a 500 mL round bottom flask, 2.78 g of EtLP6 intermediate (about 6.4 mmol) and 0.6 g of paraformaldehyde (about 20 mmol) were dissolved in 225 mL of dichloromethane, and the EtLP6 intermediate was completely dissolved by stirring at room temperature. Then 1 mL of boron trifluoride etherate was added, and the solution was quenched with water after 30 minutes of reaction at room temperature. When the solution was ink green, 3 g of sodium bicarbonate was added to adjust the pH to neutral, and the solution was continuously stirred for 1 hour. Then the lower organic phase was extracted using a 500 mL separatory funnel, and the extraction was performed three times. Then 4 g of anhydrous sodium sulfate was added to remove the residual water in the organic phase, and 10 g of silica gel powder was added and dispersed uniformly by ultrasonic. The solvent was completely removed by rotary evaporation at 35 °C in a water bath, at a rotation speed of 110 revolutions per minute and a vacuum degree of -12 pascal, to obtain a crude product. The silica gel powder, crude product, anhydrous sodium sulfate, and quartz sand were filled into a chromatographic column, and petroleum ether: ethyl acetate (volume ratio = 8:1) was selected as the developing agent to separate the components on the silica gel plate. Then 1000 mL of petroleum ether: dichloromethane (volume ratio = 1:4) was used as the eluent to elute the EtLP6. The obtained eluent was rotary evaporated to obtain a yellow oily substance, which was purified by adding 1.5 mL of acetone and standing for 2 hours. Then the white solid was obtained, which was dried in a vacuum oven at 120 degrees for 12 hours to obtain 0.972 g of EtLP6 (yield about 34%).

[0035] 2. Preparation of solvent-free EtLP6a material:

[0036] Into a 20 mL glass bottle, 0.5 g of EtLP6 was added, 8 mL of dichloromethane was added, and the mixture was heated to 100 °C to completely dissolve the EtLP6. Then 8 mL of n-hexane was added, and the mixture was slowly evaporated at room temperature for 2 days to obtain a block-shaped crystal. The surface adhered liquid was washed off with methanol, and the powder was obtained by grinding the crystal in a mortar after heating in a vacuum oven at 120 degrees for 12 hours.

[0037] 3. Preparation of solid-state charge transfer complex EtLP6a-TFTN, as shown in Figure 1

[0038] ​Mix 0.223 g of EtLP6 a (0.25 mmol) and 0.1 g of tetrafluorotetracyanophenyl (TFTN) (purchased from Angene Chemical, CAS No: 1835-49-0, Item No: D040524) (0.5 mmol) in a marble mortar, and grind the mixture with a pestle at room temperature until the color of the mixture changes obviously. The white EtLP6 a and TFTN turn into light yellow mixed powder after grinding, indicating the formation of solid-state charge transfer complex.

[0039] Example 2, Application of solid-state charge transfer complex EtLP6 a-TFTN material in detecting 1,3-dioxane and 1,4-dioxane:

[0040] Take two 20 mL glass bottles, and add 2 mL of 1,3-dioxane and 1,4-dioxane respectively into each of the two bottles. Then, put two 2 mL sample glass bottles containing 10 mg of light yellow EtLP6 a-TFTN powder into the two 20 mL glass bottles respectively for gasochromic performance test. Observe the obvious color change after 2 hours.

[0041] After 2 hours, take the two 2 mL sample glass bottles out of the two 20 mL glass bottles, and take a small amount of EtLP6 a-TFTN powder with a small spoon and place it on the weighing paper. Take a photo in a small photo studio with the same background and lighting to record the color change of EtLP6 a-TFTN, as shown in Figure 2

[0042] It can be seen that the solid-state charge transfer complex EtLP6 a-TFTN exhibits a switch-type gasochromic effect under the vapor stimulation of 1,3-dioxane and 1,4-dioxane isomers, thereby realizing the rapid detection of the two dioxane isomers. Specifically, EtLP6 a-TFTN will change from light yellow powder to dark yellow powder under the vapor stimulation of 1,3-dioxane, and from light yellow powder to white powder under the vapor stimulation of 1,4-dioxane.

[0043] Performance test:

[0044] 1. Characterize the properties of EtLP6 a-TFTN prepared in Example 1. Measure the ultraviolet absorption spectrum and ultraviolet reflection spectrum using an ultraviolet-visible spectrophotometer, and perform PXRD test using a powder diffractometer to analyze whether grinding will change the crystal phase. The test results are shown in Figures 3 to 5 , specifically:

[0045] ​The changes in characteristic absorption bands caused by CT interaction were detected by ultraviolet absorption spectroscopy. When white EtLP6α and TFTN were mixed and ground in a 1:2 molar ratio, a significant color change occurred, resulting in a pale yellow powder mixture. Solid-state ultraviolet-visible absorption spectroscopy showed that EtLP6α-TFTN had a distinct absorption band in the visible light region, which contrasts sharply with the absence of an absorption band in the visible light range for single-component EtLP6α and TFTN. Figure 3 );

[0046] By measuring the change in reflected light intensity with wavelength, the ultraviolet reflectance spectrum can be obtained, and the characteristics of material color change can be analyzed. When white EtLP6α and TFTN are mixed and ground in a 1:2 molar ratio to form a pale yellow EtLP6α-TFTN powder, the solid ultraviolet reflectance spectrum can clearly reflect this color change. Compared with the almost no reflectance characteristics of single-component EtLP6α and TFTN in the visible light range, EtLP6α-TFTN powder exhibits obvious reflectance characteristics in the visible light region. Figure 4 This corroborates the changes in characteristic absorption bands observed in ultraviolet absorption spectra, together revealing the differences in the optical properties of materials under different states;

[0047] To investigate the effect of EtLP6α and TFTN co-grinding on the crystal structure, PXRD tests were performed, and the results are as follows: Figure 5 As shown, the PXRD spectrum of EtLP6α-TFTN formed after mixing and grinding is different from that of EtLP6α and TFTN physically mixed. Only the diffraction peak intensities of EtLP6α and TFTN have changed, and no new crystal phase has been formed.

[0048] 2. For the gas-induced color change experiment of EtLP6α-TFTN prepared in Example 1 under the vapor stimulation of two dioxane isomers, 1H NMR spectra were measured using a nuclear magnetic resonance spectrometer to compare the compositional changes of EtLP6α-TFTN powder before and after color change. Ultraviolet absorption and ultraviolet reflectance spectra were measured using a UV-Vis spectrophotometer. PXRD tests were performed using a powder diffractometer to analyze the changes in the crystal structure of EtLP6α-TFTN before and after color change. To further investigate the dynamic changes in the CT interaction between EtLP6α and TFTN under the vapor stimulation of 1,3-dioxane and 1,4-dioxane, Raman spectroscopy was used to measure the samples to capture microscopic information at the molecular vibrational level, thereby comprehensively analyzing the changes in the CT interaction between the two. The test results are as follows: Figures 6 to 12 As shown, specifically:

[0049] The results of nuclear magnetic resonance hydrogen spectrum show that 1,4-dioxane vapor is adsorbed by EtLP6a-TFTN, and the adsorption amount of 1,4-dioxane vapor can be calculated as about 3.0 mol / mol EtLP6a-TFTN Figure 6 , while EtLP6a-TFTN does not adsorb 1,3-dioxane vapor Figure 7 ;

[0050] The characteristic absorption band changes caused by CT interaction can be analyzed by ultraviolet absorption spectrum analysis, from Figure 8 it can be seen that the absorption peak intensity of EtLP6a-TFTN increases obviously and the peak shifts to red shift under the stimulation of 1,3-dioxane vapor, indicating that the CT interaction is enhanced, and the color is deepened; while under the stimulation of 1,4-dioxane vapor, the absorption peak intensity decreases and the peak shifts to blue shift, indicating that the CT interaction is weakened, and the color is lightened, these changes clearly show the difference of characteristic absorption band before and after color change, revealing the optical response characteristics of EtLP6a-TFTN under different vapor stimulation;

[0051] By measuring the change of reflected light intensity with wavelength, the ultraviolet reflection spectrum can be obtained, and then the characteristics of color change of the material can be analyzed, from Figure 9 it can be seen that the reflectivity of EtLP6a-TFTN decreases as a whole under the stimulation of 1,3-dioxane vapor, especially in the visible light region, indicating that the color of the material is deepened, and the CT interaction is enhanced; while under the stimulation of 1,4-dioxane vapor, the reflectivity increases as a whole, the color is lightened, and the CT interaction is weakened, the change of ultraviolet reflection spectrum corresponds to the change of color of the material and the change of CT interaction;

[0052] In order to explore the changes of crystal structure of EtLP6a-TFTN before and after color change, PXRD test was carried out, and the results are as follows Figure 10 , Figure 11PXRD pattern of EtLP6@TFTN is obtained by long crystal, the PXRD pattern of simulated EtLP6@TFTN (Simulated EtLP6@TFTN) derived by mercury software is roughly the same as the PXRD pattern of EtLP6α-TFTN@1,3-dioxane which color changes to deep yellow under the stimulation of 1,3-dioxane vapor, indicating that EtLP6α-TFTN will gradually change to the co-crystal of EtLP6@TFTN under the stimulation of 1,3-dioxane vapor; while the PXRD pattern of EtLP6α-TFTN@1,4-dioxane which color changes to white under the stimulation of 1,4-dioxane vapor is also different from the PXRD pattern of original EtLP6α-TFTN, indicating that the crystal structure of EtLP6α-TFTN also changes after adsorbing 1,4-dioxane vapor, forming a new crystal structure, the PXRD pattern of EtLP6α@1,4-dioxane measured after EtLP6α adsorbs 1,4-dioxane is roughly the same as the PXRD pattern of EtLP6α-TFTN@1,4-dioxane which color changes to white after adsorbing 1,4-dioxane vapor, and the significant TFTN diffraction peak reappears in the PXRD pattern of EtLP6α-TFTN@1,4-dioxane, indicating that the CT interaction between EtLP6α and TFTN is destroyed under the stimulation of 1,4-dioxane vapor, EtLP6α-TFTN dissociates, and after dissociation, due to the continuous adsorption of 1,4-dioxane by EtLP6α, the crystal structure also changes to EtLP6α@1,4-dioxane;

[0053] Raman spectrum is used to prove the difference between EtLP6α-TFTN@1,3-dioxane and EtLP6α-TFTN@1,4-dioxane CT interaction, the test results of Raman spectrum are as follows Figure 12 As shown in the Raman spectrum of EtLP6α-TFTN, the typical absorption peak of CN group of TFTN (about 2238 cm -1The peak intensity of EtLP6α-TFTN@1,3-dioxane is significantly lower than that of monocomponent TFTN. This may be because the strong external charge transfer (CT) interaction between EtLP6 and TFTN produces a shielding effect. In the Raman spectrum of EtLP6α-TFTN@1,3-dioxane, the peak intensity of the typical absorption peak of the CN group of TFTN is further reduced compared to EtLP6α-TFTN. This indicates that the external charge transfer (CT) interaction between EtLP6α and TFTN is enhanced under the vapor stimulation of 1,3-dioxane, and a eutectic transformation towards EtLP6-TFTN is achieved. Conversely, the Raman spectrum of EtLP6α-TFTN@1,4-dioxane shows a strong absorption peak related to the CN group, similar to that of monocomponent TFTN. This proves that the adsorption of 1,4-dioxane by EtLP6α-TFTN greatly weakens the CT interaction between EtLP6α-TFTN, thus significantly reducing the shielding effect.

[0054] 3. Crystal growth and crystal structure analysis of EtLP6@1,3-dioxane (1,3-dioxane):

[0055] 1.5 mg of EtLP6 was added to a 2 mL glass vial, followed by 1 mL of 1,3-dioxane solution. The solution was heated on a hot plate at 50 °C for 3 minutes until completely dissolved. The solution was then allowed to evaporate slowly at room temperature, resulting in smooth, crack-free blocky crystals. Single-crystal XRD analysis of the grown crystals revealed the crystal structure of EtLP6@1,3-dioxane (e.g., EtLP6@1,3-dioxane). Figure 13 As shown in the figure, analysis of the crystal structure using Mercury software revealed that EtLP6 and 1,3-dioxane are bonded in a molar ratio of 1:1. 75% of the 1,3-dioxane is encapsulated within the cavities formed by EtLP6, while 25% of the 1,3-dioxane is bonded to EtLP6 via external complexation. Furthermore, the analysis showed that the 1,3-dioxane and EtLP6 are bonded through multiple weak interactions.

[0056] 4. Crystal growth and crystal structure analysis of EtLP6@1,4-dioxane (1,4-dioxane):

[0057] 1.5 mg of EtLP6 was added to a 2 mL glass vial, followed by 1 mL of 1,4-dioxane solution. The solution was heated on a hot plate at 50 °C for 3 minutes until completely dissolved. The solution was then allowed to evaporate slowly at room temperature, resulting in smooth, crack-free blocky crystals. Single-crystal XRD analysis of the grown crystals revealed the crystal structure of EtLP6@1,4-dioxane (e.g., EtLP6@1,4-dioxane). Figure 14As shown in the figure, using mercury software to analyze the crystal structure found that EtLP6 combined with 1,4-dioxane in a molar ratio of 1:3, 1 / 3 of 1,4-dioxane was wrapped in the cavity formed by EtLP6, 2 / 3 of 1,4-dioxane combined with EtLP6 in the form of cavity outside complexation, and it was analyzed that 1,4-dioxane combined with EtLP6 through multiple weak interactions.

[0058] 5. Crystal growth and crystal structure analysis of EtLP6@TFTN:

[0059] 1.0 mg of EtLP6 and 1.0 mg of TFTN were loaded into a 2 ml glass sample bottle, 1.5 mL of methylcyclohexane solution was added, and it was completely dissolved on a heating plate at 60°C for 5 minutes, then it was placed at room temperature to slowly evaporate, finally a blocky crystal with smooth surface and no cracks was obtained, the grown crystal was analyzed by single crystal XRD, and the crystal structure of EtLP6@TFTN was obtained (as shown in the figure). Figure 15 As shown in the figure, using mercury software to analyze the crystal structure found that EtLP6 combined with 1,4-dioxane in a molar ratio of 1:3, 1 / 3 of 1,4-dioxane was wrapped in the cavity formed by EtLP6, 2 / 3 of 1,4-dioxane combined with EtLP6 in the form of cavity outside complexation, and it was analyzed that 1,4-dioxane combined with EtLP6 through multiple weak interactions.

[0060] The above only describes the preferred embodiments of the present application and is not intended to limit the present application, any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A solid state charge transfer complex, characterized in that, The solid-state charge transfer complex is EtLP6α-TFTN, which takes ethyl oblique [6] arene EtLP6 as electron donor and electron-deficient aromatic tetrakisfluorotetracyanoethylene as electron acceptor, and has a powder X-ray diffraction pattern as shown in Figure 5; The chemical structural formula of the ethyl oblique [6] arene EtLP6 is as follows: 。 2. A process for the preparation of a solid charge transfer complex as claimed in claim 1, characterized in that, The method comprises the following steps: Synthesizing EtLP6; Preparation of solvent-free EtLP6α; After mixing EtLP6α and tetrakisfluorotetracyanoethylene, grinding is performed until the color of the mixture changes from white to light yellow, indicating the formation of the solid-state charge transfer complex, and the molar ratio of the EtLP6α and tetrakisfluorotetracyanoethylene is 1:1.8-2.

2.

3. The method of claim 2, wherein the solid-state charge transfer complex is prepared by the process comprising: The step of synthesizing EtLP6 specifically comprises: 1,4-p-dichlorobenzene, p-diethoxybenzene and dichloromethane are stirred at room temperature until completely dissolved, aluminum chloride is added, and the reaction is carried out at room temperature. Water is added to quench the reaction, and the lower organic phase is extracted, and the water is removed. Silica gel powder is added and ultrasonically dispersed, and heated in a water bath. The crude product is obtained by rotary evaporation, and then separated, eluted, dried by rotary evaporation, and dried by rotary evaporation to obtain the EtLP6 intermediate. The EtLP6 intermediate and paraformaldehyde are dissolved in dichloromethane, and the EtLP6 intermediate is completely dissolved by stirring at room temperature. Then, boron trifluoride ether is added, and the reaction is carried out at room temperature until the solution is dark green. Water is added to quench the reaction, and the pH is adjusted to neutral. The lower organic phase is extracted, and the water is removed. Silica gel powder is added and ultrasonically dispersed, and heated in a water bath. The crude product is obtained by rotary evaporation, and then separated, eluted, dried by rotary evaporation, and dried by rotary evaporation to obtain the EtLP6.

4. The method of claim 2, wherein the solid-state charge transfer complex is prepared by the process comprising: The step of preparing solvent-free EtLP6α specifically comprises: Dichloromethane is added to EtLP6 and heated to completely dissolve it. n-Hexane is added, and it is evaporated at room temperature to obtain a block-shaped crystal. The surface adhered liquid is washed off with methanol, and the powder is obtained by grinding after drying.

5. The method for preparing the solid charge transfer composite according to claim 2, characterized in that, The molar ratio of the EtLP6α and tetrakisfluorotetracyanoethylene is 1:

2.

6. The solid-state charge transfer complex of claim 1 in detecting 1,3-dioxane and 1,4-dioxane.

7. Use according to claim 6, characterized in that, The solid-state charge transfer complex changes from light yellow powder to dark yellow powder under the stimulation of 1,3-dioxane vapor; The solid-state charge transfer complex changes from light yellow powder to white powder under the stimulation of 1,4-dioxane vapor.

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