Synthesis method and memory device of ferrocene-based D-A type multi-ary conjugated small molecule

Abstract

The application discloses a synthesis method of a D-A type multi-ary conjugated small molecule based on ferrocene, and comprises the following steps: taking a ferrocene-based compound and a bromophenyl compound as raw materials, taking a palladium complex as a catalyst, and performing a heating reaction in an organic solvent; after the reaction is completed, an intermediate is prepared through extraction, column chromatography and recrystallization; taking the obtained intermediate and a 4-pyridine boronic acid compound as raw materials, taking a palladium complex as a catalyst, and performing a heating reaction in an organic solvent; after the reaction is completed, a D-A type multi-ary conjugated small molecule is prepared through cooling, extraction, column chromatography and recrystallization. The application further discloses a sandwich structure memory device and applies the sandwich structure memory device to super-high-density information storage. The small molecule material prepared by the application can not only realize ternary information storage performance, but also greatly improve the stability of the device through the stable redox cycle of the ferrocene group, thereby realizing long-time stable super-high-density information storage.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of functional semiconductor materials and electronic information, and relates to a synthesis method of a D-A type multi-ary conjugated small molecule based on ferrocene and a storage device. BACKGROUND

[0002] In the field of information storage technology, resistive random access memory (ReRAM) has attracted much attention in recent years. With the advantages of high storage density, low power consumption, fast read-write speed, and good compatibility with existing semiconductor processes, ReRAM has become a strong competitor for the next generation of storage technology. Early research on ReRAM was mainly focused on exploring materials with resistance transition characteristics, and the research focused on transition metal oxides such as titanium dioxide (TiO2) and zinc oxide (ZnO). At the same time, through the combination of different materials and structural design, such as the construction of a simple metal-oxide-metal (MIM) structure, the basic framework of ReRAM was gradually built. It was found that some organic small molecule / polymer materials also exhibited significant changes in resistance value after applying voltage.

[0003] Currently, more and more functional semiconductor materials, such as small molecule materials, transition metal oxides, organic metal complexes, polymers, organic conjugated frameworks, graphene oxides, two-dimensional semiconductor materials, and perovskite materials, are applied to the research of multi-ary storage field. At the same time, mechanisms such as charge trapping, charge transfer, redox, conformational transition, and filament conduction are also applied to explain the phenomenon of multi-ary storage. However, considering the advantages of functional small molecule compounds, such as clear molecular structure, good synthesis repeatability, good thin film accumulation, and consistent photoelectric performance of small molecules obtained from different batches, the main focus of the research is still on carefully designing the structure of small molecules, so as to obtain multi-ary storage materials and devices with long stability and good reproducibility.

[0004] However, the multi-ary storage devices based on small molecule materials reported at present still have many problems in stability and reproducibility, which is mainly due to the problems of thermal stability and electrochemical stability of organic small molecule materials, so that the subsequent electrical performance test and stability test cannot meet the ideal requirements. SUMMARY

[0005] The purpose of the present application is to overcome the problems of insufficient thermal stability and electrochemical stability of small molecule materials in current multi-ary storage devices, and to provide a synthesis method of a D-A type multi-ary conjugated small molecule based on ferrocene and a storage device, thereby realizing multi-ary storage materials and devices with long-term stability and high device reproducibility.

[0006] Ferrocene has high thermal and chemical stability, unique sandwich structure, excellent redox activity and excellent electrochemical stability. At the same time, the integration of redox and charge transfer mechanism into a single small molecule material provides a new strategy for subsequent organic multi-state memory devices with good stability and high reproducibility.

[0007] Technical scheme: The first scheme of the present application is to provide a synthesis method of D-A type multi-state conjugated small molecule based on ferrocene, comprising the following steps:

[0008] (1) taking ferrocene-based compound and bromophenyl compound as raw materials, taking palladium complex as catalyst, heating reaction in organic solvent, after the reaction is completed, extraction, column chromatography and recrystallization to prepare an intermediate;

[0009] (2) taking the intermediate obtained in step (1) and 4-pyridine boronic acid compound as raw materials, taking palladium complex as catalyst, heating reaction in organic solvent, after the reaction is completed, cooling, extraction, column chromatography and recrystallization to prepare a D-A type multi-state conjugated small molecule.

[0010] Further, in step (1), the ferrocene-based compound is 1,1'-diferrocene halide, selected from one of 1,1'-dibromoferrocene and 1,1'-diiodoferrocene; the bromophenyl compound is 4-bromophenyl boronic acid compound, selected from one of 4-bromophenyl boronic acid and 4-bromophenyl boronic acid pinacol ester; or,

[0011] The ferrocene-based compound is 1,1'-diferrocene boronic acid compound, selected from one of 1,1'-diferrocene diboronic acid and 1,1'-diferrocene diboronic acid pinacol ester; the bromophenyl compound is 4-bromophenyl halide compound, selected from one of 1,4-dibromobenzene and 1-bromo-4-iodobenzene.

[0012] The synthesis route of the organic small molecule semiconductor material is shown in the following formula (I) or (II):

[0013] (I),

[0014] (II).

[0015] Further, in step (1), the palladium complex catalyst is one of bis(triphenylphosphine)palladium(II) dichloride, 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride and tetrakis(triphenylphosphine)palladium; the organic solvent is one of ethylene glycol monomethyl ether and ethylene glycol dimethyl ether.

[0016] Further, in step (1), the molar ratio of 1,1'-ferrocene halide and 4-bromophenylboronic acid compound is 1:(2~5); the added amount of the palladium complex catalyst is 1~5 mol% of 1,1'-ferrocene halide; the molar ratio of 1,1'-ferrocene boronic acid compound and 4-bromophenyl compound is 1:(2~5); the added amount of the palladium complex catalyst is 1~5 mol% of 1,1'-ferrocene boronic acid compound.

[0017] Further, in step (1), the reaction is carried out in an oxygen-free environment, the reaction temperature is 70~90℃, and the reaction time is 120~360 hours.

[0018] Further, in step (2), the 4-pyridyl boronic acid compound is selected from one of 4-pyridyl boronic acid and 4-pyridyl boronic acid pinacol ester.

[0019] Further, in step (2), the palladium complex catalyst is selected from one of bis(triphenylphosphine)palladium(II) dichloride, 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride, and tetrakis(triphenylphosphine)palladium; and the organic solvent is selected from one of tetrahydrofuran, 1,4-dioxane, and toluene.

[0020] Further, in step (2), the molar ratio of the intermediate and the 4-pyridyl boronic acid compound is 1:(2~5); and the added amount of the palladium complex catalyst is 1~5 mol% of the intermediate.

[0021] Further, in step (2), the reaction is carried out in an oxygen-free environment, the reaction temperature is 70~90℃, and the reaction time is 48~72 hours.

[0022] The second aspect of the present application provides a memory device prepared from a ferrocene-based D-A type multi-ary conjugated small molecule prepared based on the synthesis method of the ferrocene-based D-A type multi-ary conjugated small molecule, comprising the following steps:

[0023] (1) dissolving the synthesized D-A type multi-ary conjugated small molecule in an organic solvent, heating and ultrasonicating, and obtaining a spin coating solution after the solution is clear and transparent;

[0024] (2) extruding 4 drops of the spin coating solution prepared in step (1) to the surface of a clean indium tin oxide glass through a syringe equipped with a filter head with a pore size of 0.22 microns, and obtaining a uniform organic thin film layer by spin coating using a spin coater after dropping is completed;

[0025] (3) placing the organic thin film prepared in step (2) into a high vacuum evaporation instrument, and evaporating an aluminum electrode with a thickness of 100 nm on the surface thereof, to obtain an electric storage device with a sandwich structure.

[0026] Advantages: Compared with the prior art, the present application has the following remarkable advantages:

[0027] (1) The D-A type multi-ary conjugated small molecule has a simple structure, and the molecular skeleton is a linear and rigid conjugated planar structure, which is conducive to the close and orderly accumulation of molecules, and no long alkyl chain is introduced in the molecular skeleton to interfere with the orderly accumulation of molecules.

[0028] (2) The ferrocene introduced in the D-A type multi-ary conjugated small molecule has high light, heat and chemical stability, which is conducive to improving the chemical stability of the synthesized small molecule, and further solves the problem of poor long-term stability in the multi-ary storage device based on small molecules.

[0029] (3) The ferrocene introduced in the D-A type multi-ary conjugated small molecule has extremely excellent electrochemical stability and outstanding redox activity, and the core group is a ferrocene group. Under the action of an electric field, ferrocene (Fe) can be oxidized to ferrocenium ion (Fe + ), thereby changing the resistance of the molecule and ultimately affecting the conductivity of the molecular thin film and realizing the storage performance. At the same time, the pyridine group introduced at the end of the molecule is a typical electron-withdrawing group, which can induce intermolecular charge transfer under the action of an electric field, and can further change the conductivity of the molecular thin film.

[0030] (4) The D-A type multi-ary conjugated small molecule integrates the redox and charge transfer mechanisms organically, not only improves the reproducibility and stability of the device, but also provides a new idea for the design of subsequent multi-ary small molecules. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 It is the nuclear magnetic hydrogen spectrum (H NMR) diagram of the intermediate 【3】 in Example 1; 1

[0032] Figure 2 It is the nuclear magnetic hydrogen spectrum (H NMR) diagram of the organic D-A type multi-ary conjugated small molecule of Example 18; 1

[0033] Figure 3 It is the theoretical simulation of the organic D-A type multi-ary conjugated small molecule of Example 18;

[0034] Figure 4 It is the X-ray diffraction (XRD) diagram of the organic thin film prepared in Example 32;

[0035] Figure 5 It is the diagram of the "sandwich" structure of the storage device prepared in Example 32; ​​

[0036] Figure 6 The electrical performance chart obtained for the test example;

[0037] Figure 7 The long-term stability performance chart obtained for the test example. DETAILED DESCRIPTION

[0038] The application will be further described in conjunction with the drawings and specific embodiments so that those skilled in the art can better understand and implement the present application, but the embodiments are not intended to limit the present application.

[0039] Example 1

[0040] The synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0041] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocene-bisboronic acid (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether solution, and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium (II) dichloride (15 mg, 0.02 mmol) to the above reaction system, stir well, and perform nitrogen replacement on the reaction system three times. Then warm the system to 70 ℃ under nitrogen protection, and continue to react at this temperature for 120 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phases, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml), and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporator under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatographic separation on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.68 g of orange-red intermediate 【3】, with a calculated yield of about 69%.

[0042] APPENDIX Figure 1The 1H NMR spectrum of the intermediate 3 of the organic D-A type multi-valency conjugated small molecule can be seen from the 1H NMR spectrum that the peaks at δ 4.62 and 4.23 ppm can be attributed to the C-H on the ferrocene five-membered ring, and the peaks at δ 7.23-7.11 ppm can be attributed to the hydrogen atoms on the aromatic ring.

[0043] Example 2

[0044] The synthesis of the intermediate 3 of the organic D-A type multi-valency conjugated small molecule is as follows:

[0045] Dissolve 1-bromo-4-iodobenzene (1.41 g, 5.00 mmol) and 1,1'-ferrocene bisboronic acid (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether solution, and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium (II) dichloride (15 mg, 0.02 mmol) to the above reaction system, stir well, and replace the reaction system with nitrogen three times. Then warm the system to 70 ℃ under nitrogen protection, and continue to react at this temperature for 120 hours. After the reaction is completed, the temperature is lowered to room temperature, and during this period, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phase, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.75 g of an orange-red intermediate 3, with a calculated yield of about 76%.

[0046] Example 3

[0047] The synthesis of the intermediate 3 of the organic D-A type multi-valency conjugated small molecule is as follows:

[0048] Dissolve 1-bromo-4-iodobenzene (2.82 g, 10.00 mmol) and 1,1'-ferrocene- bis(boronic acid) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether, stir well to obtain a clear transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, continue to stir for 30 minutes. Under the atmosphere of nitrogen, add catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) to the above reaction system, stir well, and then nitrogen replace the reaction system for three times. Then warm the system to 70 ℃ under the protection of nitrogen, and continue to react at this temperature for 120 hours. After the reaction is completed, the temperature is lowered to room temperature, and during this period, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phase, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and then remove the organic solvent by rotary evaporator under reduced pressure, and concentrate to orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.76 g of orange-red intermediate 【3】, with a calculated yield of about 77%.

[0049] Example 4

[0050] The synthesis of intermediate 【3】 of the organic D-A type multi-ary conjugated small molecule is as follows:

[0051] Dissolve 1-bromo-4-iodobenzene (1.41 g, 4.00 mmol) and 1,1'-ferrocene- bis(boronic acid) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (30 mg, 0.04 mmol) to the above reaction system, stir well, and then perform nitrogen replacement on the reaction system three times. Then, under nitrogen protection, warm the system to 70 ℃, and continue to react the reaction system at this temperature for 120 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phases, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml), and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse the powder in n-hexane solvent until a slurry is formed, then filter, and continue to recrystallize to obtain 0.78 g of an orange-red intermediate 【3】, with a calculated yield of about 79%.

[0052] Example 5

[0053] The synthesis of the intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0054] Dissolve 1-bromo-4-iodobenzene (1.41 g, 4.00 mmol) and 1,1'-ferrocene- bis(boronic acid) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (75 mg, 0.10 mmol) to the above reaction system, stir well, and then perform nitrogen replacement on the reaction system three times. Then, under nitrogen protection, warm the system to 70 ℃, and continue to react the reaction system at this temperature for 120 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phases, and then dry the organic phase with saturated NH4Cl solution (100 mL), water (100 mL), and saturated brine (100 mL) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and then remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse the powder in n-hexane solvent until a slurry is formed, then filter, and continue to recrystallize to obtain 0.71 g of an orange-red intermediate 【3】, with a calculated yield of about 72%.

[0055] Example 6

[0056] Synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule, with the specific steps as follows:

[0057] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocene- bis(boronic acid) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) to the above reaction system, stir well, and then perform nitrogen replacement on the reaction system three times. Then, under nitrogen protection, warm the system to 80 ℃, and continue to react at this temperature for 120 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phases, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml), and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.72 g of an orange-red intermediate 【3】, with a calculated yield of about 73%.

[0058] Example 7

[0059] The synthesis of the intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0060] To a solution of 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocenediboronic acid (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether was added sodium hydroxide in water (3.0 M, 5 mL) and stirred until a clear solution was obtained. The catalyst, 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) was added to the solution and stirred until a clear solution was obtained. The solution was purged with nitrogen three times. The solution was then heated to 90 °C under a nitrogen atmosphere and stirred for 120 hours. The solution was then cooled to room temperature and stirred until the solution was cooled to room temperature. Deionized water was added to the solution and the solution was extracted with ethyl acetate. The aqueous layer was extracted with ethyl acetate three times. The organic layers were combined and washed with saturated NH4C1 solution (100 mL), water (100 mL), and saturated brine (100 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to an orange-red solid. The solid was dissolved in chloroform and chromatographed on silica gel using chloroform as the eluent. The eluted solvent was removed under reduced pressure to give an orange powder. The powder was dispersed in n-hexane under sonication until a slurry was formed. The slurry was filtered and recrystallized to give 0.80 g of the orange-red intermediate 【3】. The yield was calculated to be about 81%.

[0061] Example 8

[0062] The synthesis of the intermediate 【3】 of the organic D-A type multi-valent conjugated small molecule was carried out according to the following procedure:

[0063] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocene- bis(boronic acid) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) to the above reaction system, stir well, and then perform nitrogen replacement on the reaction system three times. Then, under nitrogen protection, warm the system to 70 ℃, and continue to react the reaction system at this temperature for 240 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phases, and then dry the organic phase with saturated NH4Cl solution (100 mL), water (100 mL), and saturated brine (100 mL) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and then remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse the powder in n-hexane solvent until a slurry is formed, then filter, and continue to recrystallize to obtain 0.78 g of an orange-red intermediate 【3】, with a calculated yield of about 79%.

[0064] Example 9

[0065] The synthesis of the intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0066] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocene- bis(boronic acid) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether, stir well to obtain a clear transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, continue to stir for 30 minutes. Under the atmosphere of nitrogen, add catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) to the above reaction system, stir well, and then nitrogen replace the reaction system for three times. Then warm the system to 70 ℃ under the protection of nitrogen, and continue to react at this temperature for 360 hours. After the reaction is completed, the temperature is lowered to room temperature, and during this period, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phase, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and then remove the organic solvent by rotary evaporator under reduced pressure, and concentrate to orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.81 g of orange-red intermediate 【3】, with a calculated yield of about 82%.

[0067] Example 10:

[0068] The synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0069] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocenediyl bis(pinacolate) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol monomethyl ether and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst palladium (II) bis(triphenylphosphine) dichloride (14 mg, 0.02 mmol) to the above reaction system, stir well, and then perform nitrogen replacement on the reaction system three times. Then, under nitrogen protection, warm the system to 70 ℃, and continue to react the reaction system at this temperature for 120 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phases, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml), and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse the powder in n-hexane solvent until a slurry is formed, then filter, and continue to recrystallize to obtain 0.65 g of an orange-red intermediate 【3】, with a calculated yield of about 66%.

[0070] Example 11:

[0071] Synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule, with the specific steps as follows:

[0072] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocenediyl bis(pinacolato)diboron (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether and stir well to obtain a clear and transparent solution system, then add an aqueous solution of sodium hydroxide (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add a catalyst, dichlorobis(triphenylphosphine)palladium(II) (14 mg, 0.02 mmol) to the reaction system, stir well, and perform nitrogen replacement three times on the reaction system. Then, under nitrogen protection, warm the system to 70 °C, and continue to react at this temperature for 120 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate. Extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phases, and then wash and extract the organic phase with saturated NH4Cl solution (100 mL), water (100 mL), and saturated brine (100 mL) once. Dry the obtained organic phase with anhydrous sodium sulfate, and then remove the organic solvent under reduced pressure using a rotary evaporator. Concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel using chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse the powder in n-hexane solvent until a slurry is formed, then filter, and continue to recrystallize to obtain 0.52 g of an orange-red intermediate 【3】, with a calculated yield of about 53%.

[0073] Example 12:

[0074] Synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule, with the specific steps as follows:

[0075] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocene- bis(boronic acid) (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether, stir well to obtain a clear transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst tetrakis(triphenylphosphine)palladium (23 mg, 0.02 mmol) to the above reaction system, stir well, and then nitrogen replace the reaction system three times. Then warm the system to 70 ℃ under nitrogen protection, and continue to react at this temperature for 120 hours. After the reaction is completed, the temperature is lowered to room temperature, and during this period, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phase, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, then remove the organic solvent under reduced pressure with a rotary evaporator, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.50 g of an orange-red intermediate 【3】, with a calculated yield of about 51%.

[0076] Example 13:

[0077] The synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0078] Dissolve 1-bromo-4-iodobenzene (1.13 g, 4.00 mmol) and 1,1'-ferrocenediboronic acid pinacol ester (0.88 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether, stir well to obtain a clear transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, continue to stir for 30 minutes. Under the atmosphere of nitrogen, add the catalyst tetrakis(triphenylphosphine)palladium (23 mg, 0.02 mmol) to the above reaction system, stir well, and then nitrogen replace the reaction system for three times. Then warm the system to 70 ℃ under the protection of nitrogen, and continue to react at this temperature for 36 hours. After the reaction is completed, the temperature is lowered to room temperature, and during this period, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phase, and finally dry the organic phase with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) and extract once, dry the obtained organic phase with anhydrous sodium sulfate, and then remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.87 g of orange-red intermediate 【3】, with a calculated yield of about 88%.

[0079] Example 14:

[0080] The synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0081] Dissolve 1,4-dibromobenzene (0.94 g, 4.00 mmol) and 1,1'-ferrocene- dicarboxylic acid bisboronic acid (0.54 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether solution, and stir well to obtain a clear and transparent solution system, then add sodium hydroxide aqueous solution (3.0 M, 5 mL) to the solution system, and continue to stir for 30 minutes. Under a nitrogen atmosphere, add the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) to the above reaction system, stir well, and perform nitrogen replacement on the reaction system three times. Then warm the system to 70 ℃ under nitrogen protection, and continue to react at this temperature for 120 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with ethyl acetate solvent, extract the obtained aqueous phase with 50 mL of ethyl acetate three times, combine the obtained organic phase, and finally wash and extract the organic phase with saturated NH4Cl solution (100 mL), water (100 ml), and saturated brine (100 ml) once, dry the obtained organic phase with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse it in n-hexane solvent until a slurry is formed, then filter and continue to recrystallize to obtain 0.68 g of an orange-red intermediate 【3】, with a calculated yield of about 69%.

[0082] Example 15:

[0083] The synthesis of the intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0084] A clear transparent solution was obtained by dissolving 4-bromophenylboronic acid (0.80 g, 4.00 mmol) and 1,1'-dibromoferrocene (0.69 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether with vigorous stirring, then adding an aqueous solution of sodium hydroxide (3.0 M, 5 mL) to the solution, and continuing to stir for 30 minutes. Under a nitrogen atmosphere, the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) was added to the reaction system, and the reaction system was stirred well and replaced with nitrogen three times. Then the temperature of the system was raised to 70 °C under nitrogen protection, and the reaction system was continued to react at this temperature for 120 hours. After the reaction was completed, the temperature was lowered to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and extracted with ethyl acetate solvent, the obtained aqueous phase was extracted with 50 mL of ethyl acetate three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted once with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml), the obtained organic phase was dried with anhydrous sodium sulfate, and then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to an orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as the eluent. The eluted solvent was subsequently removed under reduced pressure to obtain an orange powder, which was then ultrasonically dispersed in n-hexane solvent until a slurry was formed, then filtered and recrystallized to obtain 0.61 g of an orange-red intermediate 【3】, with a calculated yield of about 62%.

[0085] Example 16:

[0086] The synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0087] To a solution of 4-bromophenylboronic acid pinacol ester (1.13 g, 4.00 mmol) and 1,1'-dibromoferrocene (0.69 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether was stirred well to obtain a clear and transparent solution system, then sodium hydroxide aqueous solution (3.0 M, 5 mL) was added to the solution system, and stirring was continued for 30 minutes. Under a nitrogen atmosphere, the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) was added to the above reaction system, stirred well, and the reaction system was replaced with nitrogen three times. Then the temperature of the system was raised to 70 ℃ under nitrogen protection, and the reaction system continued to react at this temperature for 120 hours. After the reaction was completed, the temperature was lowered to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and extracted with ethyl acetate solvent, the obtained aqueous phase was extracted with 50 mL of ethyl acetate three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted once with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml), the obtained organic phase was dried with anhydrous sodium sulfate, then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was subsequently removed under reduced pressure to obtain an orange powder, which was then ultrasonically dispersed in n-hexane solvent until a slurry was formed, then filtered and recrystallized to obtain 0.63 g of orange-red compound 【3】, with a calculated yield of about 64%.

[0088] Example 17:

[0089] The synthesis of intermediate 【3】 of the organic D-A type multi-valued conjugated small molecule is as follows:

[0090] To a solution of 4-bromophenylboronic acid pinacol ester (1.13 g, 4.00 mmol) and 1,1'-dibromoferrocene (0.86 g, 2.0 mmol) in 40 mL of ethylene glycol dimethyl ether was stirred well to obtain a clear and transparent solution system, then sodium hydroxide aqueous solution (3.0 M, 5 mL) was added to the solution system, and stirring was continued for 30 minutes. Under a nitrogen atmosphere, the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (15 mg, 0.02 mmol) was added to the above reaction system, stirred well, and the reaction system was replaced with nitrogen three times. Then the temperature of the system was raised to 70 ℃ under nitrogen protection, and the reaction system continued to react at this temperature for 120 hours. After the reaction was completed, the temperature was lowered to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and extracted with ethyl acetate solvent, the obtained aqueous phase was extracted with 50 mL of ethyl acetate three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted once with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml), the obtained organic phase was dried with anhydrous sodium sulfate, then the organic solvent was removed by rotary evaporator under reduced pressure, concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was subsequently removed under reduced pressure to obtain an orange powder, which was then ultrasonically dispersed in n-hexane solvent until a slurry was formed, then filtered and recrystallized to obtain 0.69 g of orange-red intermediate 【3】, with a calculated yield of about 70%.

[0091] Example 18:

[0092] The synthesis of organic D-A type multi-valued conjugated small molecule 【5】 is as follows:

[0093] Dissolve 4-pyridine boronic acid (0.42 g, 3.4 mmol) and compound 3 (0.85 g, 1.7 mmol) in 20 mL of toluene and 8 mL of ethanol, then add an aqueous solution of sodium hydroxide (3.0 M, 12 mL) to the solution system, and continue stirring for 30 minutes. Under a nitrogen atmosphere, add a catalyst tetra (triphenylphosphine) palladium (19 mg, 0.017 mmol) to the above reaction system, stir well, and replace the reaction system with nitrogen three times. Then warm the system to 70 ℃ under nitrogen protection, and continue the reaction at this temperature for 48 hours. After the reaction is completed, the temperature is lowered to room temperature, and during this period, the reaction mixture is continuously stirred until it cools to room temperature. Then add an appropriate amount of deionized water to the reaction system, and extract with dichloromethane. The obtained aqueous phase is extracted with 50 mL of dichloromethane three times, the obtained organic phase is combined, and finally the organic phase is washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once. The obtained organic phase is dried with anhydrous sodium sulfate, and then the organic solvent is removed by rotary evaporation under reduced pressure, and concentrated to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, the eluted solvent is removed under reduced pressure to obtain an orange powder, which is then ultrasonically dispersed in petroleum ether solvent until a slurry is formed, and then filtered to obtain 0.58 g of red conjugated small molecule 【5】, with a calculated yield of about 70%.

[0094] Figure 1 is a schematic diagram of an organic D-A type multi-state conjugated small molecule. Figure 2 Figure 2 is a proton nuclear magnetic resonance spectrum of an organic D-A type multi-state conjugated small molecule. Figure 3 Figure 3 is a theoretical simulation diagram of an organic D-A type multi-state conjugated small molecule. 1 As can be seen from the H NMR diagram, the doublet with the strongest polarization ability at a chemical shift of 8.59-8.58 ppm is the hydrogen atom corresponding to the pyridine functional group near the N atom in the small molecule, and the continuous peaks at 7.45-7.31 ppm are the aromatic hydrogen atoms corresponding to the pyridine and phenyl functional groups in the small molecule. Finally, the two nuclear magnetic peaks at chemical shifts of 4.58 and 4.32 ppm are the two groups of hydrogen atoms corresponding to the five-membered ring of ferrocene in the small molecule. As can be seen from the theoretical simulation diagram, the pyridine group at the end of the skeleton of the organic D-A type multi-state conjugated small molecule is a typical electron-withdrawing group, and under the electric field stimulus, charge transfer from metal to ligand (MLCT) and charge transfer from electron donor to electron acceptor can occur in the molecular skeleton, and theoretically, multi-state storage performance can be achieved.

[0095] Example 19:

[0096] Synthesis of organic D-A type multi-valency conjugated small molecule 【5】 is as follows:

[0097] Dissolve 4-pyridineboronic acid pinacol ester (0.70 g, 3.4 mmol) and compound 3 (0.85 g, 1.7 mmol) in 20 mL of toluene and 8 mL of ethanol, then add an aqueous solution of sodium hydroxide (3.0 M, 12 mL) to the solution system, and continue stirring for 30 minutes. Under a nitrogen atmosphere, add a catalyst of tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) to the above reaction system, stir well, and perform nitrogen replacement three times on the reaction system. Then, under nitrogen protection, warm the system to 70 °C, and continue the reaction at this temperature for 48 hours. After the reaction is completed, reduce the temperature to room temperature, continue to stir the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with dichloromethane solvent, extract the obtained aqueous phase with 50 mL of dichloromethane three times, combine the obtained organic phase, and finally wash and extract the organic phase with saturated NH4Cl solution (100 mL), water (100 mL), and saturated brine (100 mL) once, dry the obtained organic phase with anhydrous sodium sulfate, and remove the organic solvent by rotary evaporation under reduced pressure, concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse it in petroleum ether solvent until a slurry is formed, then filter to obtain 0.60 g of red conjugated small molecule 【5】, with a calculated yield of about 72%.

[0098] Example 20:

[0099] Synthesis of organic D-A type multi-valency conjugated small molecule 【5】 is as follows:

[0100] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of 1,4-dioxane and 8 mL of ethanol, and then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and the stirring was continued for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, and after the stirring was uniform, the reaction system was replaced with nitrogen for three times. Then the temperature of the system was raised to 70 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was reduced to room temperature, and in this period, the stirring of the reaction mixture was continued until it was cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and extracted with dichloromethane solvent, the obtained aqueous phase was extracted with 50 mL of dichloromethane for three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) for one time, the obtained organic phase was dried with anhydrous sodium sulfate, and then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was removed under reduced pressure, and orange powder was obtained, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, and then filtered to obtain 0.55 g of red conjugated small molecule 【5】, and the yield was about 66%.

[0101] Example 21:

[0102] The synthesis of organic D-A type multi-valued conjugated small molecule 【5】 is as follows:

[0103] Compound 3 (0.85 g, 1.7 mmol) in 20 mL of tetrahydrofuran and 8 mL of ethanol, then added to this solution system of sodium hydroxide aqueous solution (3.0 M, 12 mL), continue to stir for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenyl phosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, after stirring well, and the reaction system was replaced with nitrogen three times. Then the temperature of the system was raised to 70 ℃ under the protection of nitrogen, the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was reduced to room temperature, during which the reaction mixture was continuously stirred until it cooled to room temperature, then added to the reaction system with an appropriate amount of deionized water, and extracted with dichloromethane solvent, the resulting aqueous phase was extracted with 50 mL of dichloromethane three times, the organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, the organic phase was dried with anhydrous sodium sulfate, then the organic solvent was removed by rotary evaporator under reduced pressure, concentrated to orange-red solid. The solid residue was dissolved in chloroform, chromatographed on silica gel with chloroform as eluent. Subsequently, the eluted solvent was removed under reduced pressure to obtain an orange powder, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then filtered to obtain 0.51 g of red conjugated small molecule 【5】, with a calculated yield of about 62%.

[0104] Example 22:

[0105] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0106] Compound 3 (0.85 g, 1.7 mmol) in 20 mL of toluene and 8 mL of ethanol, then added sodium hydroxide aqueous solution (3.0 M, 12 mL) to the solution system, and continued to stir for 30 minutes. Under the atmosphere of nitrogen, the catalyst bis(triphenylphosphine)palladium(II) dichloride (12 mg, 0.017 mmol) was added to the above reaction system, and stirred uniformly, and the reaction system was replaced with nitrogen three times. Then the temperature of the system was raised to 70 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was reduced to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and extracted with dichloromethane solvent, the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, the obtained organic phase was dried with anhydrous sodium sulfate, and then the organic solvent was removed by rotary evaporator under reduced pressure, concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. Subsequently, the eluted solvent was removed under reduced pressure to obtain orange powder, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then filtered to obtain 0.44 g of red conjugated small molecule 【5】, with a calculated yield of about 52%.

[0107] Example 23:

[0108] The synthesis of organic D-A type multi-valued conjugated small molecule 【5】 is as follows:

[0109] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, and then an aqueous solution of sodium hydroxide (3.0 M, 12 mL) was added to the solution system, and stirring was continued for 30 minutes. Under a nitrogen atmosphere, the catalyst 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride (12 mg, 0.017 mmol) was added to the above reaction system, and after stirring uniformly, the reaction system was replaced with nitrogen three times. Then the temperature of the system was raised to 70 °C under nitrogen protection, and the reaction system was continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was lowered to room temperature, and in this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and extracted with dichloromethane solvent, and the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, and the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, and the obtained organic phase was dried with anhydrous sodium sulfate, and then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was subsequently removed under reduced pressure to obtain orange powder, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, and then filtered to obtain 0.46 g of red conjugated small molecule 【5】, with a calculated yield of about 56%.

[0110] Example 24:

[0111] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0112] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and stirring was continued for 30 minutes. Under a nitrogen atmosphere, the catalyst tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, and after stirring uniformly, the reaction system was replaced with nitrogen three times. Then the temperature of the system was raised to 80 ℃ under nitrogen protection, and the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was lowered to room temperature, and in this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and dichloromethane solvent was used for extraction, the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, the obtained organic phase was dried with anhydrous sodium sulfate, then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. Subsequently, the eluted solvent was removed under reduced pressure to obtain orange powder, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then filtered to obtain 0.50 g of red conjugated small molecule 【5】, with a calculated yield of about 60%.

[0113] Example 25:

[0114] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0115] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and the stirring was continued for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, and the reaction system was stirred uniformly and replaced with nitrogen for three times. Then the temperature of the system was raised to 90 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was reduced to room temperature, and in this period, the reaction mixture was continuously stirred until it was cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and dichloromethane solvent was used for extraction, and the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, and the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, and the obtained organic phase was dried with anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was removed under reduced pressure, and orange powder was obtained, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then filtered to obtain 0.54 g of red conjugated small molecule 【5】, and the yield was about 64%.

[0116] Example 26:

[0117] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0118] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and the stirring was continued for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, and the reaction system was stirred uniformly and replaced with nitrogen for three times. Then the temperature of the system was raised to 90 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 72 hours. After the reaction was completed, the temperature was reduced to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and dichloromethane solvent was used for extraction, and the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, and the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, and the obtained organic phase was dried with anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was removed under reduced pressure, and an orange powder was obtained, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then filtered to obtain 0.52 g of red conjugated small molecule 【5】, and the yield was about 62%.

[0119] Example 27:

[0120] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0121] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and the stirring was continued for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, and the reaction system was stirred uniformly and replaced with nitrogen for three times. Then the temperature of the system was raised to 90 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 64 hours. After the reaction was completed, the temperature was reduced to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and dichloromethane solvent was used for extraction, and the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, and the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, and the obtained organic phase was dried with anhydrous sodium sulfate, and then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was removed under reduced pressure, and an orange powder was obtained, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then filtered to obtain 0.51 g of red conjugated small molecule 【5】, and the yield was about 61%.

[0122] Example 28:

[0123] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0124] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and the stirring was continued for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, and the reaction system was stirred uniformly and replaced with nitrogen for three times. Then the temperature of the system was raised to 70 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was reduced to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and dichloromethane solvent was used for extraction, the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, the obtained organic phase was dried with anhydrous sodium sulfate, then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was removed under reduced pressure, and orange powder was obtained, then it was ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then it was filtered to obtain 0.66 g of red conjugated small molecule 【5】, and the yield was about 76%.

[0125] Example 29:

[0126] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0127] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and the stirring was continued for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenylphosphine palladium (19 mg, 0.017 mmol) was added to the above reaction system, and the reaction system was stirred uniformly and replaced with nitrogen for three times. Then the temperature of the system was raised to 70 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was reduced to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and dichloromethane solvent was used for extraction, the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, the obtained organic phase was dried with anhydrous sodium sulfate, then the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was removed under reduced pressure, and orange powder was obtained, then it was ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then it was filtered to obtain 0.57 g of red conjugated small molecule 【5】, and the yield was about 68%.

[0128] Example 30:

[0129] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0130] Compound 3 (0.85 g, 1.7 mmol) were dissolved in 20 mL of toluene and 8 mL of ethanol, then sodium hydroxide aqueous solution (3.0 M, 12 mL) was added to the solution system, and the stirring was continued for 30 minutes. Under the atmosphere of nitrogen, the catalyst tetrakis triphenylphosphine palladium (38 mg, 0.034 mmol) was added to the above reaction system, and the reaction system was stirred uniformly and replaced with nitrogen for three times. Then the temperature of the system was raised to 70 ℃ under the protection of nitrogen, and the reaction system continued to react at this temperature for 48 hours. After the reaction was completed, the temperature was reduced to room temperature, and during this period, the reaction mixture was continuously stirred until it cooled to room temperature, then an appropriate amount of deionized water was added to the reaction system, and dichloromethane solvent was used for extraction, and the obtained aqueous phase was extracted with 50 mL of dichloromethane three times, and the obtained organic phase was combined, and finally the organic phase was washed and extracted with saturated NH4Cl solution (100 mL), water (100 ml) and saturated brine (100 ml) once, and the obtained organic phase was dried with anhydrous sodium sulfate, and the organic solvent was removed by rotary evaporator under reduced pressure, and concentrated to orange-red solid. The solid residue was dissolved in chloroform, and chromatographed on silica gel with chloroform as eluent. The eluted solvent was removed under reduced pressure, and an orange powder was obtained, which was then ultrasonically dispersed in petroleum ether solvent until a slurry was formed, then filtered to obtain 0.61 g of red conjugated small molecule 【5】, and the yield was about 73%.

[0131] Example 31:

[0132] The synthesis of organic D-A type multi-ary conjugated small molecule 【5】 is as follows:

[0133] Dissolve 4-pyridineboronic acid pinacol ester (0.70 g, 3.4 mmol) and compound 3 (0.85 g, 1.7 mmol) in 20 mL of toluene and 8 mL of ethanol, then add an aqueous solution of sodium hydroxide (3.0 M, 12 mL) to the solution system, and continue stirring for 30 minutes. Under a nitrogen atmosphere, add a catalyst of tetrakis triphenylphosphine palladium (95 mg, 0.085 mmol) to the above reaction system, stir thoroughly, and then replace the reaction system with nitrogen three times. Then, under nitrogen protection, warm the system to 70 °C, and continue the reaction at this temperature for 48 hours. After the reaction is complete, reduce the temperature to room temperature, continue stirring the reaction mixture until it cools to room temperature, then add an appropriate amount of deionized water to the reaction system, and extract with dichloromethane. Extract the resulting aqueous phase with 50 mL of dichloromethane three times, combine the organic phases, and then wash and extract the organic phase with saturated NH4Cl solution (100 mL), water (100 mL), and saturated brine (100 mL) once. Dry the organic phase with anhydrous sodium sulfate, then remove the organic solvent by rotary evaporation under reduced pressure, and concentrate to an orange-red solid. Dissolve the solid residue in chloroform, and perform chromatography on silica gel with chloroform as the eluent. Subsequently, remove the eluted solvent under reduced pressure to obtain an orange powder, then ultrasonically disperse the powder in petroleum ether solvent until a slurry is formed, and then filter to obtain 0.59 g of red conjugated small molecule 【5】 with a calculated yield of about 71%.

[0134] Example 32:

[0135] The preparation of an organic “sandwich” structure memory device is as follows:

[0136] First, weigh 12 mg of 1,1'-bis(4-phenylpyridyl)ferrocene small molecule and disperse it in 1 ml of diphenylmethane solvent to control the concentration to 12 mg / mL, and ultrasonically dissolve it to form a clear and transparent solution system. Second, use a syringe to extract the solution system, then install an organic filter head with a diameter of 0.22 μm on the syringe. Slowly drop 4 drops of the solution system onto the surface of the ITO glass. Then, set the initial spin coating speed of the spin coater to 400 revolutions per minute, and the spin coating time to 15 seconds; set the subsequent spin coating speed of the spin coater to 2500 revolutions per minute, and the spin coating time to 30 seconds. After spin coating is complete, place the obtained organic thin film in a vacuum oven for solvent evaporation treatment, set the oven temperature to 60 °C, and the vacuum degree to 10 -3 Torr, and dry for 12 hours. Finally, cover the surface of the organic thin film with a mask with a pore size of 120 microns, then place the organic thin film with the mask in a high vacuum evaporation instrument, set the vacuum degree to 10 -6Tol, the evaporation rate of the current control aluminum particles is 1 angstrom per second by adjusting the vacuum evaporation equipment, the thickness of the aluminum electrode is set to 100 nanometers, and the memory device with a "sandwich" structure as shown in the accompanying Figure 5 Figure a) is a photograph of a memory device with a "sandwich" structure prepared from an organic D-A type multi-valued conjugated small molecule, and Figure 5 Figure b) is a simulation diagram of a memory device with a "sandwich" structure prepared from an organic D-A type multi-valued conjugated small molecule, where 9 is a glass substrate, 10 is an ITO layer, 11 is a molecular layer, which is an organic thin film prepared from an organic D-A type multi-valued conjugated small molecule, and 12 is an aluminum electrode. Figure 5

[0137] Figure a) is a photograph of a memory device with a "sandwich" structure prepared from an organic D-A type multi-valued conjugated small molecule, and Figure 4 Figure b) is a simulation diagram of a memory device with a "sandwich" structure prepared from an organic D-A type multi-valued conjugated small molecule, where 9 is a glass substrate, 10 is an ITO layer, 11 is a molecular layer, which is an organic thin film prepared from an organic D-A type multi-valued conjugated small molecule, and 12 is an aluminum electrode.

[0138] Test Example:

[0139] The memory device with a "sandwich" structure prepared in Example 32 was placed on a semiconductor test platform, and during the multi-valued storage performance and device reproducibility tests, the probe applied a negative scan voltage of 0 ~ -5V and a positive scan voltage of 0 ~ 5V; during the long-term stability test of the device, the probe applied a constant direct current voltage of -0.5V, -2V, and -4V for 10000 seconds.

[0140] Figure a) is a photograph of a memory device with a "sandwich" structure prepared from an organic D-A type multi-valued conjugated small molecule, and​Figure 6 The test results of the memory device of "sandwich" structure show that the small molecule of 1,1'-bis(4-phenylpyridyl)ferrocene can exhibit typical ternary storage performance, and the attached Figure 7 The display device can also exhibit excellent long-time stability, and each conductive state thereof can still be maintained under continuous power-on for 10000 seconds.

[0141] Obviously, the above embodiments are merely illustrative examples and are not intended to limit the embodiments. Based on the above description, other different forms of changes or variations can be made by those of ordinary skill in the art. All embodiments do not need to be exhausted here. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A memory device, comprising: A ferrocene-based D-A type multi-ary conjugated small molecule is prepared by the following steps: (1) dissolving the D-A type multi-ary conjugated small molecule in an organic solvent, heating and ultrasonicating, and obtaining a spin coating solution after the solution is clear and transparent; the structure of the D-A type multi-ary conjugated small molecule is shown as follows: ； (2) extruding 4 drops of the spin coating solution prepared in step (1) to the surface of a clean indium tin oxide glass through a syringe provided with a filter head with a pore size of 0.22 microns, and obtaining a uniform organic thin film layer by spin coating using a spin coater after dropping; (3) placing the organic thin film prepared in step (2) into a high vacuum evaporation instrument, and evaporating an aluminum electrode with a thickness of 100 nm on the surface thereof, to obtain an electric storage device with a sandwich structure.

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