CN101492442A - Complex diaryl fluorene material, preparation and application method thereof - Google Patents

Abstract

The complex diaryl fluorene material and its preparation and application methods belong to the field of organic photoelectric material science and technology, specifically a non-planar complex bi-polycyclic heteroaryl fluorene material and a Friedel-Crafts preparation method, and use this type of material as a hole transport The material, the electron transport material and the three-primary-color light-emitting material are applied in organic electronic fields such as organic flash memory devices and organic light-emitting displays. 2) It is in an amorphous glass state, showing high thermal stability and glass transition temperature; (3) It has the advantages of high hole or electron mobility. Complex diarylfluorene materials will become organic optoelectronic functional materials with commercial potential.

Description

Complex diarylfluorene materials and methods for their preparation and application

technical field

The invention belongs to the technical field of organic photoelectric materials. It specifically relates to a non-planar polycyclic heteroaromatic organic semiconductor material and its preparation method, and relates to the application of these materials in the fields of organic electroluminescence, photovoltaic cells, organic electrical storage, organic nonlinear optics, chemical and biological sensing, and organic lasers. Applications.

technical background

Since 1987, the Tang Research Group of Kodak Company in the United States [Tang, C.W.; Van Slyke, S.A.Appl.Phys. Lett. 1987, 57, 913.] and the University of Cambridge in 1990 [Burruges, J.H.; Bradley, D.D.C.; Brown, A.B.; Marks, R.N.; Mackay, K.; Friend, R.H.; Burn, P.L.; Holmes, A.B.Nature 1990, 347, 539.] published thin-film organic electroluminescent devices (Organic Light -emitting Diodes) and Polymeric Light-emitting Diodes (Polymeric Light-emitting Diodes), organic flat panel display has become another generation of market-oriented display products after liquid crystal display. At the same time, other organic electronics and optoelectronic industries, including fields such as organic field effect transistors, organic solar cells, nonlinear optics, biosensing and lasers, and nonlinear optical materials are also moving toward marketization. The advantages of organic and plastic electronics lie in the low cost of material preparation, simple process, and the flexibility and plasticity of general-purpose polymers. Therefore, the development of new organic optoelectronic information materials with practical market potential has attracted the attention and investment of many scientists from different disciplines in universities at home and abroad, as well as research institutions and companies. So far, the development of new and highly stable carrier transport materials and light-emitting materials has become a key factor to improve the efficiency and lifetime of organic electronics, electro-optic and optoelectronic devices.

So far, optoelectronic materials containing 9-position fluorene modified by diaryl groups as core construction exhibit high thermal stability and high glass transition temperature, so they have become a promising class of practical organic optoelectronic materials, and have formed considerable articles and patents. However, there are few patents on using phenylfluorene or heterofluorene as a capping unit to modify easily crystallized organic semiconductor materials to make them highly stable amorphous materials, and the preparation methods are complicated. Therefore, the present invention discusses the development of a series of end-capped photoelectric materials containing heteroatom aromatics such as sulfur, nitrogen, and oxygen through simple processing methods, and has the advantages of high solubility, blocking chromophore aggregation, or stabilizing structural chains. The material will have a wide application space in organic electronics, optoelectronics, or optoelectronic materials.

Contents of the invention

Technical problem: The purpose of the present invention is to propose a non-planar polycyclic heteroaromatic organic semiconductor material with high environmental stability and morphological stability, as well as special photoelectric properties. In addition, the application of this kind of materials in the field of organic electronics such as organic electroluminescence, organic laser, photovoltaic cells and organic electrical storage devices is pointed out.

Technical solution: A complex diaryl fluorene material of the present invention is characterized in that the material uses non-planar aryl fluorene or azafluorene as a capping group heteropolycyclic aromatic hydrocarbon conjugated molecule, and has the following structure:

Compound material I

In the formula: R ₁ and R ₂ are the same or different when they appear, and are hydrogen or straight, branched or cyclic alkyl chains or alkoxy chains with 1 to 22 carbon atoms; n, m are 0, Any number in 1, 2, 3, 4; X is carbon or nitrogen; Ar is a heteroatom-containing polycyclic aromatic hydrocarbon conjugated structural unit; Ar is specifically one of the following structures:

In the formula: l is any number among 0, 1, 2, 3, 4; Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ are hydrogen or one of the following structures:

Ar in the compound material I is an aromatic ring containing oxygen, sulfur or nitrogen, and has the following structure:

The compound material I has the following structure:

Prepared by Friedel-Crafts reaction, the reaction is as follows: wherein,

Approach 1 Friedel-Crafts Reaction as the Final Capping Process to Realize Nonplanar Polycyclic Heteroaromatic Organic Semiconductors Containing Phenylfluorene

Method 2 Friedel-Crafts Reaction as the Initial Capping Process to Realize Nonplanar Polycyclic Heteroaromatic Organic Semiconductors Containing Phenylfluorene

The Friedel-Crafts reaction conditions are specifically that heteroaromatics and tertiary alcohols are mixed in a molar ratio, and at a temperature of 25-150 degrees Celsius, hydrochloric acid/glacial acetic acid, methanesulfonic acid/carbon tetrachloride, and trifluoromethanesulfonic acid are added in equimolar ratios. / carbon tetrachloride, or boron trifluoride ether complex / dichloromethane catalyst, the reaction time is between 30 minutes and 48 hours.

Complex diaryl fluorene materials are applied to organic semiconductor devices for information storage, in which the structure of the device is a transparent anode/electric bistable layer/cathode, in which the complex bi-polycyclic heteroaryl fluorene material is used as an electric bistable layer by vacuum evaporation It is prepared by plating, solution spin coating or inkjet printing, and the cathode is prepared by vacuum coating technology.

Complex diarylfluorene materials are used in light-emitting diode devices or photovoltaic cell devices, where the structure of the device is transparent anode/hole transport layer/light-emitting layer/electron transport layer/cathode, wherein the light-emitting layer is omitted in the photovoltaic cell device, complex The bipolycyclic heteroaryl fluorene material is used as an active material in one of the hole transport layer, light emitting layer or electron transport layer.

Beneficial effects: Characterize the aromatics by elemental analysis, infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), chromatography-mass on-line (GCMS), matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS), and gel chromatography (GPC). Based on the structure of fluorene materials, the thermal stability of the materials was tested by thermogravimetric analysis and differential thermal analysis, and their electrochemical properties were characterized by cyclic voltammetry.

Among them, the thermogravimetric analysis and differential thermal analysis tests of this type of material show high thermal stability and glass transition temperature, so devices composed of this type of material can effectively eliminate defects such as crystallization and pinholes; cyclic voltammetry The electrochemical properties characterized by the method showed that the oxidation potential did not change significantly, and the good hole or electron injection ability of polycyclic heteroaromatics was maintained. The quantum efficiency of the modified luminescent material is clearly improved. Therefore, such materials can be used as efficient hole transport materials, electron transport materials, light emitting materials, heterojunction doping materials and host materials.

This type of molecular material can be applied in the field of organic electronics such as organic semiconductor devices. Compound material I is suitable for organic light emitting diode devices, organic electrical storage devices, organic solar cells, organic laser diode devices, organic field effect transistors, and the like.

On this basis, a preliminary light-emitting diode device was designed to evaluate the carrier transport properties of non-planar polycyclic heteroaromatic organic semiconductor materials. The structure of the device is transparent anode/compound material I/quinoline aluminum/cathode, wherein compound material I is prepared as a hole transport layer by vacuum evaporation, solution spin coating or inkjet printing, and quinoline aluminum and cathode are prepared by vacuum coating technical preparation. Experimental results show that these non-planar polycyclic heteroaromatic organic semiconductor materials exhibit stable and efficient hole transport capabilities.

The main advantages of the present invention are:

1. The Friedel-Crafts reaction has simple synthesis steps and mild conditions;

2. High thermal stability and glass transition temperature.

3. Maintain high hole or electron mobility.

Description of drawings:

Figure 1. Thermal analysis characterization of 2,5-bis(9-phenyl-fluoren-9-yl)thiophene. Wherein Fig. 1 (a) represents thermogravimetric analysis result; Fig. 1 (b) represents DSC differential calorimetry scanning analysis result.

Figure 2.5, Thermal analysis and characterization of 5″-bis(9-phenyl-fluoren-9-yl)-2,2′:5′,2″-trithiophene. Wherein Fig. 2 (a) represents thermogravimetric analysis result; Fig. 2 (b) represents DSC differential calorimetry scanning analysis result.

Figure 3. Thermal analysis characterization of 2-(9-phenyl-fluoren-9-yl)-spiro[indene[2,1-b]thiophene-8,9'-fluorene]. Wherein Fig. 3 (a) represents thermogravimetric analysis result; Fig. 3 (b) represents DSC differential calorimetry scanning analysis result.

Figure 4. Thermal analytical characterization of tris(4-(9-phenyl-fluoren-9-yl)phenyl)amine. Wherein Fig. 4 (a) represents thermogravimetric analysis result; Fig. 4 (b) represents DSC differential calorimetry scanning analysis result.

Figure 5.5, Voltage-brightness curve and device electroluminescence spectrum of 5"-bis(9-phenyl-fluoren-9-yl)-2,2':5',2"-trithiophene. Among them, Fig. 5(a) voltage-brightness curve; Fig. 5(b) shows the emission spectrum of ALQ3.

Figure 6. Voltage-brightness curve and device electroluminescence spectrum of tris(4-(9-phenyl-fluoren-9-yl)phenyl)amine. Among them, Fig. 6(a) voltage-brightness curve; Fig. 6(b) shows the emission spectrum of ALQ3.

Detailed ways

The non-planar complex diarylfluorene organic semiconductor material of the present invention is an organic semiconductor material with arylfluorene or heteroarylfluorene as a capping group, and has the following structure:

Example 1. Preparation of thiophene material post-modified with 9-phenyl-fluorene unit:

9-Phenyl-fluoren-9-ol

Take bromo-benzene (2.1mmol) and magnesium (0.502g, 2.1mmol) to react to generate Grignard reagent, and react with fluorenone (2.1mmol) dissolved in 16mL tetrahydrofuran at 60°C for 24 hours, a large amount of white precipitate is formed, and finally add saturated Chromatic NHCl ₄ converts the Grignard salt to alcohol. After the reaction was completed, ether was extracted, dried and rotary evaporated, and purified on a silica gel column with a mixed solvent of petroleum ether:dichloromethane (3:2) to obtain a slightly pale yellow solid tertiary alcohol (yield 90%). GC-MS (EI-m/z): 258.1 (M ⁺ ). ¹ H NMR (400MHz, CDCl ₃ , ppm): δ7.691-7.672 (d, J=7.6Hz, 2H), 7.406-7.325 (m , 6H), 7.292-7.236 (m, 5H), 2.508 (s, 1H). ¹³ C NMR (CDCl ₃ , ppm): δ150.658, 143.391, 139.82, 129.339, 128.698, 128.459, 127.462, 125.633, 125.037, 120.343, 83.85.

2,5-bis(9-phenyl-fluoren-9-yl)thiophene

Dissolve 9-phenyl-fluorene-9-alcohol and thiophene in dichloromethane at a ratio of 2:1, add boron trifluoride-ether complex dropwise at room temperature for 30 minutes, add ethanol and water to quench Quenching reaction, dichloromethane extraction, drying rotary evaporation, petroleum ether silica gel column purification, recrystallization with tetrahydrofuran and petroleum ether to obtain white powder solid 2,5-bis(9-phenyl-fluorene-9-yl)thiophene (yield was 90.1%). ¹ H NMR (400MHz, CDCl ₃ , ppm): δ7.755-7.737 (d, J=7.6Hz, 4H), 7.478-7.459 (d, J=7.6Hz, 4H), 7.384-7.344 (td, J= 7.6Hz, J=1.2Hz, 4H), 7.291-7.251(td, J=7.6Hz, J=1.2Hz, 4H), 7.173(s, 5H), 6.624(s, 2H). ¹³ C NMR (CDCl ₃ , ppm): δ151.092, 148.197, 145.761, 139.998, 128.346, 127.949, 127.89, 127.768, 127.096, 126.405, 125.817, 120.367, 62.559.

Example 2, 9-phenyl-fluoren-9-ol as a capping agent to treat 2,2'-dithiophene capping material preparation:

5,5'-bis(9-phenyl-fluoren-9-yl)-2,2'-dithiophene

Dissolve 9-phenyl-fluorene-9-ol and 2,2'-dithiophene in dichloromethane at a ratio of 2:1, add boron trifluoride-ether complex dropwise at room temperature for 30 minutes , adding ethanol and water to quench the reaction, dichloromethane extraction, drying and rotary evaporation, petroleum ether: dichloromethane silica gel column purification, recrystallization with tetrahydrofuran and petroleum ether to obtain white powder solid 5,5'-bis(9-phenyl -Fluoren-9-yl)-2,2'-dithiophene (92.1% yield). MALDI-TOF-MS (m/z): 646.2 (M ⁺ ). ¹ H NMR (400MHz, CDCl ₃ , ppm): δ7.759-7.74 (d, J=7.6Hz, 4H), 7.491-7.472 (d , J=7.6Hz, 4H), 7.392-7.352(td, J=7.2Hz, J=1.2Hz, 4H), 7.303-7.257(td, J=7.6Hz, J=1.2Hz, 4H), 7.228-7.188 (m, 10H), 6.817-6.808 (d, J=3.6Hz, 2H), 6.694-6.685 (d, J=3.6Hz2H). ¹³ C NMR (100MHz, CDCl3, ppm): δ150.865, 148.486, 145.11 , 139.956, 136.674, 128.441, 128.117, 127.961, 127.826, 127.291, 127.258, 126.267, 122.661, 120.445, 62.492.

Example 3, 9-phenyl-fluorene-9-ol as a capping agent to treat 2,2':5',2"-trithiophene capping material preparation:

5,5″-bis(9-phenyl-fluoren-9-yl)-2,2′: 5′,2″-trithiophene

Dissolve 9-phenyl-fluoren-9-ol and 2,2':5',2"-trithiophene in dichloromethane at a ratio of 2:1, and add boron trifluoride-ether dropwise at room temperature The complex was reacted for 30 minutes, added ethanol and water to quench the reaction, extracted with dichloromethane, dried and rotary evaporated, petroleum ether: dichloromethane silica gel column purification, recrystallized with tetrahydrofuran and petroleum ether to obtain a white powder solid 5,5″- Bis(9-phenyl-fluoren-9-yl)-2,2': 5',2"-trithiophene (81.2% yield). MALDI-TOF-MS (m/z): 728.2 (M ⁺ ). ¹ HNMR (400MHz, CDCl ₃ , ppm): δ7.774-7.755(d, J=7.6Hz, 4H), 7.519-7.5(d, J=7.6Hz, 4H), 7.404-7.367(t, J =7.6Hz, 4H), 7.32-7.283(t, J=7.6Hz, 4H), 7.271-7.215(m, 10H), 6.899-6.886(dd, J=4.0Hz, J=1.6Hz, 2H), 6.868 -6.864 (d, J=1.6Hz, 2H), 6.76-6.746 (dd, J=3.6Hz, J=1.6Hz, 2H). ¹³ C NMR (CDCl ₃ , ppm): δ150.853, 148.8, 145.017, 136.329, 136.153, 128.491, 128.188, 128.009, 127.847, 127.423, 127.342, 126.254, 124.095, 122.935, 120.49, 139.974, 62.525.

Example 4, 9-phenyl-fluoren-9-ol as a capping agent for the preparation of capping materials for triphenylamine:

N,N-Diphenyl-4-(9-phenyl-fluoren-9-yl)aniline

Dissolve 9-phenyl-fluorene-9-alcohol and triphenylamine in dichloromethane at 1:1 equivalent, and add a few drops of boron trifluoride. Ether complex to react for 30 minutes at room temperature, add ethanol and Quenching the reaction with water, extracting with dichloromethane, drying and rotary evaporation, using a mixed solvent of petroleum ether:dichloromethane as the eluent for silica gel column purification, recrystallization with tetrahydrofuran and petroleum ether to obtain a white powder solid N,N-diphenyl - 4-(9-Phenyl-fluoren-9-yl)aniline (92.5% yield). GC-MS (EI-m/z): 485 (M ⁺ ).

Example 5, 9-phenyl-fluoren-9-ol as a capping agent for the preparation of capping materials for triphenylamine:

N,N-bis(-4-(9-phenyl-fluoren-9-yl)phenyl)aniline

Dissolve 9-phenyl-fluorene-9-alcohol and triphenylamine in dichloromethane at 2:1 equivalent, and add a few drops of boron trifluoride. Ether complex to react for 30 minutes at room temperature, add ethanol and Quench the reaction with water, extract with dichloromethane, dry and rotary evaporate, petroleum ether: the mixed solvent of dichloromethane is used as the silica gel column purification of the eluent, recrystallize with tetrahydrofuran and petroleum ether to obtain light yellow powder solid N, N-bis( -4-(9-Phenyl-fluoren-9-yl)phenyl)aniline (91% yield). MALDI-TOF-MS (m/z): 725.4 (M ⁺ ).

Example 6, 9-phenyl-fluoren-9-ol as a capping agent for the preparation of capping materials for triphenylamine:

Tris(4-(9-phenyl-fluoren-9-yl)phenyl)amine

Dissolve 9-phenyl-fluorene-9-alcohol and triphenylamine in dichloromethane at a ratio of 3:1, add a few drops of boron trifluoride-ether complex dropwise at room temperature for 30 minutes, add ethanol and Quenching the reaction with water, extracting with dichloromethane, drying and rotary evaporating, petroleum ether: dichloromethane mixed solvent as the silica gel column purification of the eluent, recrystallization with tetrahydrofuran and petroleum ether to obtain light yellow powder solid three (tetra(9- Phenyl-fluoren-9-yl)phenyl)amine (90% yield). MALDI-TOF-MS (m/z): 965.3 (M ⁺ ). ¹ HNMR (400MHz, CDCl ₃ , ppm): δ7.74-7.721 (d, J=7.6Hz, 6H), 7.38-7.361 (d, J=7.6Hz, 6H), 7.346-7.308(t, J=7.6Hz, 6H), 7.259-7.219(t, J=7.6Hz, 6H), 7.174(s, 15H), 6.995-6.974(d, J =8.4Hz, 6H), 6.841-6.82 (d, J=7.6Hz, 6H). ¹³ C NMR (100MHz, CDCl ₃ , ppm): δ151.482, 146.145, 146.037, 140.218, 139.937, 128.984, 128.317, 128.229 , 127.805, 127.554, 126.706, 126.362, 123.681, 120.257, 65.131.

Example 7, Photoluminescence Spectrum and Quantum Efficiency Measurement of Non-planar Polycyclic Heteroaromatic Organic Semiconductor Materials:

The product was made into a precise 1 μM dilute solution in chloroform and flushed with argon to remove oxygen. The absorption and emission spectra were measured by Shimadzu UV-3150 ultraviolet-visible spectrometer and RF-530XPC fluorescence spectrometer. The photoluminescence spectrum is measured at the wavelength of maximum absorption of ultraviolet absorption. The photoluminescence spectrum of the solid film was carried out through a vacuum-evaporated quartz plate with a film thickness of 300 nm. The fluorescence quantum efficiencies of the solutions were measured with 1 μM 9,10-diphenylanthracene in cyclohexanone as a standard.

Example 8, thermal analysis and determination of non-planar polycyclic heteroaromatic organic semiconductor materials:

Thermogravimetric analysis (TGA)) was performed on a Shimadzu DTG-60H thermogravimetric analyzer with a heating scan rate of 10°C/min and a nitrogen flow rate of 20 cm ³ /min. Differential scanning calorimetry (DSC) was carried out on a Shimadzu DSC-60A tester. The sample was first heated at a rate of 10°C/min to a state ten degrees lower than the decomposition temperature of the sample, and then, under liquid nitrogen conditions The temperature was lowered back to the starting temperature, and the temperature was scanned at a rate of 10°C/min for the second time.

2,5-bis(9-phenyl-fluoren-9-yl)thiophene, 5,5'-bis(9-phenyl-fluoren-9-yl)-2,2'-dithiophene, 5,5" - The thermal decomposition temperature of bis(9-phenyl-fluoren-9-yl)-2,2':5',2"-trithiophene is greater than 350°C, see accompanying drawings 1, 2 and 3 respectively; The thermal decomposition temperature of tris(4-(9-phenyl-fluoren-9-yl)phenyl)amine is higher than 500° C., see accompanying drawing 4.

Embodiment 9. Electrochemical determination of non-planar polycyclic heteroaromatic organic semiconductor materials:

Electrochemical cyclic voltammetry (CV) experiments were performed on an Eco Chemie BVAUTOLAB potentiostat voltammetry analyzer using a three-electrode system, including a platinum-carbon working electrode, Ag/Ag ⁺ as a reference electrode, and a platinum wire as a counter electrode. Dichloromethane was used as a solvent in the oxidation process, tetrahydrofuran was used as a solvent in the reduction process, tetrabutylammonium hexafluorophosphine (Bu ₄ N ⁺ PF ₆ ^- ) was used as a supporting electrolyte, and the concentration was 0.1M. All electrochemical experiments were carried out under nitrogen atmosphere at room temperature, and the voltage scanning speed was 0.1V/s. Using ferrocene (FOC) as a benchmark, the HOMO and LUMO energy levels of the material can be calculated by measuring the onset voltages of the oxidation and reduction processes.

Example 10. Preparation and characterization of light-emitting devices based on non-planar polycyclic heteroaromatic organic semiconductor materials:

A light-emitting device prepared with a polyvinylcarbazole material modified after the 9-phenyl-fluorene unit as the host material, its structure is: ITO/5,5″-bis(9-phenyl-fluorene-9-yl) -2,2′:5′,2″-trithiophene (60nm) or tris(4-(9-phenyl-fluoren-9-yl)phenyl)amine (60nm)/ALQ ₃ (80nm)/Mg:Ag (250nm), where ITO is a transparent electrode with a sheet resistance of 10-20Ω/□; 5,5″-bis(9-phenyl-fluorene-9-yl)-2,2′:5′,2″-three Thiophene or three (4-(9-phenyl-fluorene-9-yl) phenyl) amine as hole transport material, film thickness 60nm, prepared by vacuum evaporation technology, ALQ3 is triquinoline aluminum, as light-emitting layer, Using vacuum evaporation technology, the film thickness is 60nm; finally, Mg:Ag cathode is evaporated to 250nm.

5,5″-bis(9-phenyl-fluoren-9-yl)-2,2′:5′,2″-trithiophene’s voltage-brightness curve and ALQ3 luminescence spectrum are shown in Figure 5; three (4 The voltage-brightness curve of -(9-phenyl-fluoren-9-yl)phenyl)amine and the luminescence spectrum of ALQ3 are shown in Figure 6.

Example 11. Preparation and characterization of electrical storage devices based on non-planar polycyclic heteroaromatic organic semiconductor materials:

First, an indium tin oxide (ITO) glass substrate was sonicated in a bath of purified water, acetone, and 2-isopropanol for 15 minutes. A toluene solution of complex diarylfluorene (10 mg/mL) was spin-coated onto an ITO substrate, and then the solvent was removed in a vacuum chamber at 10 ^-5 Torr at room temperature. The material film thickness is controlled at about 50nm. Finally, a 390-nm-thick Al electrode was realized by thermal evaporation with a mask under a pressure of 10 ^-7 Torr. Measurements were performed on devices of size 0.15 cm x 0.15 cm, 0.2 cm x 0.2 cm, and 0.4 cm x 0.4 cm. Current density-voltage curves (JV) were performed on a device with a size of 0.2cm×0.2cm. Electrical switching and switching times were performed on a Hewlett-Packard 4156A Semiconductor Parameter Analyzer and an Agilent 16440A SMU/oscilloscope, respectively.

Claims (6)

1. A complex diaryl fluorene material, characterized in that the material uses non-planar aryl fluorene or azafluorene as a capping group heteropolycyclic aromatic hydrocarbon conjugated molecule, and has the following structure:

     Compound Material I In the formula: R ₁ and R ₂ are the same or different when they appear, and are hydrogen or straight, branched or cyclic alkyl chains or alkoxy chains with 1 to 22 carbon atoms; n, m are 0, Any number in 1, 2, 3, 4; X is carbon or nitrogen; Ar is a heteroatom-containing polycyclic aromatic hydrocarbon conjugated structural unit; Ar is specifically one of the following structures:

In the formula: 1 is any number among 0, 1, 2, 3, 4; Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ are hydrogen or one of the following structures:

2. complex diaryl fluorene material according to claim 1, is characterized in that Ar is the aromatic ring containing oxygen, sulfur or nitrogen in the described compound material I, has following structure:

3. complex diaryl fluorene material according to claim 1, is characterized in that described compound material I has following structure:

4. A preparation method of complex diaryl fluorene material as claimed in claim 1, characterized in that it is prepared by adding a gram reaction, and the reaction is specifically as follows: Method 1: Fu-one-gram reaction as the final capping process to realize non-planar polycyclic heteroaromatic organic semiconductors containing phenylfluorene,

Method 2: Fu-one-gram reaction as the initial capping process to realize non-planar polycyclic heteroaromatic organic semiconductors containing phenylfluorene,

The specific reaction conditions for one gram are that heteroaromatic hydrocarbons and tertiary alcohols are mixed in a molar ratio of 6:1 to 1:3, and at a temperature of 25-150 degrees Celsius, hydrochloric acid in an equimolar ratio is added to dissolve in glacial acetic acid, and methanesulfonic acid is dissolved in tetrahydrochloride. Carbon chloride and trifluoromethanesulfonic acid are dissolved in carbon tetrachloride, or boron trifluoride ether complex is dissolved in dichloromethane catalyst, and the reaction time is between 30 minutes and 48 hours. 5. The application of a complex diaryl fluorene material as claimed in claim 1, characterized in that it is applied to an organic semiconductor device for information storage, wherein the structure of the device is a transparent anode/electric bistable layer/cathode, wherein the complex The bis-polycyclic heteroaryl fluorene material is prepared as an electric bistable layer by vacuum evaporation, solution spin coating or inkjet printing, and the cathode is prepared by vacuum coating technology. 6. The application of a complex diaryl fluorene material as claimed in claim 1, characterized in that it is applied to a light-emitting diode device or a photovoltaic cell device, wherein the structure of the device is a transparent anode/hole transport layer/light-emitting layer/electronic Transport layer/cathode, wherein the light-emitting layer is omitted in the photovoltaic cell device, and the complex bipolycyclic heteroaryl fluorene material is used as an active material in one of the hole transport layer, light-emitting layer or electron transport layer.

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