Synthesis and application of 3, 3 ', 6, 6'-tetra-substituted spirobifluorene photoelectric material

Abstract

The invention relates to the field of organic optical functional materials, in particular to a novel 3, 3 ', 6, 6'-tetrasubstituted spirobifluorene derivative organic photoelectric material and a synthesis method thereof. The structural formula of the 3, 3 ', 6, 6'-tetra-substituted spirobifluorene derivative is as shown in formula (I), a series of hole transport materials and main bodies with 3, 3 ', 6, 6'-tetra-substituted spirobifluorene structures as central skeletons are provided, the synthesis step of the hole transport materials uses a chelating auxiliary transition metal catalyzed ortho-position hydrocarbon arylation reaction or a Suzuki coupling reaction, the reaction site can be effectively controlled, and the reaction efficiency is improved. And diversification of molecular structures is realized. The molecules obtained by the invention have good photoelectric properties, thermal stability and morphology stability, have high triplet state energy level, can be adapted to red, blue, green and boron-nitrogen multiple resonance luminescent layer luminescent materials, and have important application potential in the field of organic luminescent functional materials.

Description

Technical Field

[0001] This invention rapidly constructs a series of 3,3′,6,6′-tetrasubstituted spirodifluorene derivatives using chelation-assisted transition metal-catalyzed ortho-C-H arylation reactions or Suzuki coupling reactions, and studies their photophysical properties and applications as organic optoelectronic materials in organic electroluminescent devices and organic optoelectronic conversion devices. Background Technology

[0002] Hole transport materials (HTMs) play a crucial role in organic light-emitting diode (OLED) devices due to their hole transport and electron blocking capabilities at the interface between the hole transport layer (HTL) and the emissive layer. HTMs typically require high hole mobility, good thermal stability, and suitable highest occupied molecular orbital (HOMO) energy levels to ensure a low energy barrier for injecting holes into the emissive layer, as well as suitable lowest unoccupied molecular orbital (LUMO) energy levels to block electrons from entering the HTL from the emissive layer. Most known HTMs for OLEDs are triarylamine compounds, among which 1,1-bis[4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane (TAPC) stands out due to its high hole mobility, high transparency to visible light, and high triplet energy (E0.05) for blocking triplet excitons. T =2.9eV) became one of the most classic HTMs, however, its low glass transition temperature of 74℃ (T g This determines its poor morphological stability, which is not conducive to the preparation of long-life OLEDs.

[0003] The 9,9′-spirodifluorene (SBF) structure exhibits excellent thermal stability and high Tg. g and high decomposition temperature (T d ), High E T SBF, along with its leading molecular orbital (FMO) energy levels matching adjacent layers, is widely used in OLEDs, perovskite solar cells, and organic lasers. SBF exhibits the strongest electrophilic reactivity at its C2 and C7 positions, leading to a large number of SBF-based high-performance molecular orbitals (HTMs) being C2- and C7-substituted derivatives. However, due to the para-linked electronic coupling between the substituents at C2 and C7 positions and the biphenyl fluorene, the electrophilic activity of C2- and C7-substituted SBF derivatives is significantly reduced. T The saturation of SBF molecules decreases, thus limiting their application in OLEDs. Adjusting the SBF substituents to the C3 and C6 positions, and utilizing the electronic decoupling between the substituents and fluorene biphenyl via a meta-linked mode, can improve the Eo of the target molecule. TThese materials hold promise as hole transport materials and host materials for red, green, and blue OLEDs. Furthermore, their excellent hole transport capabilities, suitable HOMO / LUMO energy levels, and good thermal stability make them a promising candidate for hole transport materials in perovskite solar cells. Currently, the design and synthesis of 3,3',6,6'-tetraarylamine-substituted spirodifluorene hole transport materials have not been reported. Summary of the Invention

[0004] The purpose of this invention is to provide a class of 3,3′,6,6′-tetrasubstituted spirodifluorene derivatives and to use them as hole transport materials or host materials in organic electroluminescent devices, or as hole transport materials in perovskite solar cells in organic photoelectric conversion devices.

[0005] The 3,3′,6,6′-tetrasubstituted spirodifluorene compound of this invention has the structure shown in Formula I:

[0006]

[0007] Wherein, Ar is selected from aryl groups with 6 to 30 carbon atoms that are substituted or unsubstituted, and heteroaryl groups with 6 to 30 carbon atoms that are substituted or unsubstituted. The heteroatoms of the heteroaryl group are preferably selected from oxygen atoms, nitrogen atoms, sulfur atoms, and selenium atoms. The substituents include, but are not limited to, hydrogen atoms, deuterium atoms, halogen atoms, trifluoromethyl groups, C1-50 alkanes, alkoxy groups, alkylsilyl groups, nitro groups, cyano groups, amino groups, substituted amino groups, ester groups, aryl groups, heteroaryl groups, and aldehyde groups.

[0008] Examples of aryl or heteroaryl groups represented by Ar, having 6 to 30 substituted or unsubstituted carbon atoms, are as follows:

[0009]

[0010]

[0011] Preferably, the hole transport material containing the 3,3′,6,6′-tetrasubstituted spirodifluorene structure includes, but is not limited to, the following structural formulas:

[0012]

[0013]

[0014]

[0015] The second objective of this invention is to provide a method for preparing the above-mentioned organic optoelectronic materials, specifically, using a chelation-assisted transition metal-catalyzed ortho-C-H arylation reaction or a Suzuki coupling reaction to rapidly construct 3,3′,6,6′-tetrasubstituted spirodifluorene derivatives. Examples of the reaction formulas are as follows:

[0016]

[0017] The third objective of this invention is to provide an application of a novel 3,3′,6,6′-tetrasubstituted spirodifluorene derivative as a hole transport material in the fabrication of OLEDs.

[0018] The fabricated organic electroluminescent device comprises, in sequence, an ITO conductive glass substrate (anode), a hole injection layer (HAT-CN), a hole transport layer (TAPC or the 3,3′,6,6′-tetrasubstituted spirodifluorene hole transport material of this invention), an electron blocking layer (TCTA), a light-emitting layer (using CBP or mCBP as the main material doped with FIrPic / Ir(mphmp)2tmd / Ir(ppy)2acac / BCz-BN as the light-emitting layer), an electron transport layer (TmPyPB), an electron injection layer (LiF), and a cathode (Al). The organic electroluminescent device is fabricated using a vacuum evaporation method. The molecular structures of some organic compounds used in this device are as follows.

[0019]

[0020] The beneficial effects of this invention are:

[0021] 1. The 3,3′,6,6′-tetrasubstituted spirodifluorene compounds provided by this invention have good photoelectric properties, thermal stability and morphological stability. The HOMO and LUMO energy levels are easy to tune and have high triplet energy, thus making them suitable for a variety of luminescent materials. They can improve exciton utilization, reduce efficiency roll-off, and have good photoelectric properties.

[0022] 2. The 3,3′,6,6′-tetrasubstituted spirodifluorene derivative material provided by the present invention can be used as a hole transport material and host material for blue, green and red OLEDs and boron nitrogen multi-resonance (BN-MR) emitting layers based on BCz-BN.

[0023] 3. The 3,3′,6,6′-tetrasubstituted spirodifluorene prepared by this invention has great potential as a hole transport material in the fields of OLED, perovskite solar cells and organic lasers, and provides a new synthetic approach for this type of hole transport material. Attached Figure Description

[0024] Figure 1 The 1H NMR spectrum of compound 2;

[0025] Figure 2 The carbon NMR spectrum of compound 2;

[0026] Figure 3 The 1H NMR spectrum of compound 3;

[0027] Figure 4 The carbon NMR spectrum of compound 3;

[0028] Figure 5 The 1H NMR spectrum of compound 4;

[0029] Figure 6 The carbon NMR spectrum of compound 4;

[0030] Figure 7 The 1H NMR spectrum of compound 5;

[0031] Figure 8 The carbon NMR spectrum of compound 5;

[0032] Figure 9 The 1H NMR spectrum of compound T02;

[0033] Figure 10 The carbon NMR spectrum of compound T02;

[0034] Figure 11 The spectrum showing the photoelectric properties of compound T02;

[0035] Figure 12 The spectrum showing the thermal stability of compound T02;

[0036] Figure 13 The OLED efficiency correlation spectrum of compound T02;

[0037] Figure 14 This is a schematic diagram of the structure of the organic electroluminescent device of the present invention. Detailed Implementation

[0038] To better understand the content of this invention, specific examples are provided below to explain the invention, but this is not intended to limit the scope of the invention.

[0039] Example: Preparation of compound T02

[0040]

[0041] Synthesis of Compound 1: 1-Bromo-4-chloro-2-iodobenzene (12.69 g) was dissolved in anhydrous THF (80 mL) and cooled to 0 °C. At this temperature, a 2 M solution of iPrMgCl in pentane (22.0 mL) was added dropwise. The resulting mixture was stirred at the same temperature for 1 hour, and 2-Bromo-4-chlorobenzaldehyde (8.72 g) was added dropwise. The reaction mixture was then stirred at 0 °C for 30 minutes, followed by heating to 75 °C and stirring for another 24 hours. After the reaction mixture cooled to room temperature, it was diluted with ethyl acetate and quenched with 6 M HCl until the aqueous layer showed litmus red. Another portion of water was added, the two phases were separated, and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were dried over sodium sulfate and concentrated under reduced pressure. The residue was dissolved in DCM, and PCC (12.93 g) was added. The reaction mixture was then stirred at room temperature for 3 hours. After the reaction was completed, the reaction mixture was diluted with ethyl acetate, filtered through a diatomaceous earth pad, and concentrated under vacuum to obtain a crude product. The crude product was then separated and purified by silica gel column chromatography to obtain a colorless solid 1 with a mass of 12.40 g and a yield of 76%. 1 H NMR (400MHz, CDCl3): δ = 7.67 (d, J = 1.6, 2H), 7.43-7.37 (m, 4H) ppm. 13 C10 NMR (100MHz, CDCl3): δ=193.65, 138.53, 137.55, 133.99, 132.27, 128.01, 121.92ppm. High-resolution mass spectrometry, ESI source, positive ion mode, molecular formula C10. 13 H6Cl2Br2NaO, theoretical values ​​428.8055, 430.8034, 432.8005, measured values ​​428.8058, 430.8032, 432.7998.

[0042]

[0043] Compound 2 was synthesized via a Suzuki coupling reaction: Under a nitrogen atmosphere, Pd(PPh3)4 (1.73 g), K2CO3 (16.56 g), compound 1 (12.23 g), 3-methoxyphenylboronic acid (5.01 g), toluene (90 mL), H2O (30 mL), and EtOH (30 mL) were charged into a Schlenk tube equipped with a magnetic stirrer. The reaction mixture was heated to 90 °C and stirred for 24 hours. After cooling to room temperature, the organic layer was extracted with ethyl acetate and washed with brine. The combined organic extracts were dried over sodium sulfate, concentrated under reduced pressure to obtain a crude product, and purified by silica gel column chromatography to give a yellow solid 2 with a mass of 12.06 g, in 87% yield. 1HNMR (400MHz, CDCl3): δ=7.24-7.22(m,2H),7.13-7.09(m,6H),6.75(dd,J1 =2.4, J2=8.4,2H),6.61(d,J=7.2,2H),6.54-6.53(m,2H),3.76(s,6H)ppm. 13 C10 NMR (100MHz, CDCl3): δ=198.95, 159.23, 142.68, 140.43, 137.64, 136.55, 131.88, 129.72, 129.29, 126.97, 121.49, 114.85, 113.24, 55.40ppm. High-resolution mass spectrometry, ESI source, positive ion mode, molecular formula C10. 27 H 20 Cl2NaO3, theoretical values ​​485.0682, 486.0715, 487.0652, measured values ​​485.0676, 486.0711, 487.0657.

[0044]

[0045] Compound 2 was synthesized via a chelation-assisted transition metal-catalyzed ortho-C-H arylation reaction: Under a nitrogen atmosphere, 1b (1.12 g), 2b (2.81 g), Pd(dba)2 (226.8 mg), N-acetyl-L-phenylalanine (165.8 mg), Ag2CO3 (1.65 g), and HFIP (10.0 mL) were added to a Schlenk tube. The reaction mixture was heated and stirred at 100 °C for 36 hours. After cooling to room temperature, the solvent was removed under reduced pressure. Then, THF (10.0 mL) and HCl (4.0 mL) were added to the Schlenk tube under air. The reaction mixture was heated at 100 °C for 12 hours. After cooling to room temperature, the reaction mixture was diluted with 20 mL of CH2Cl2, filtered through a diatomaceous earth mat, and washed with CH2Cl2. The filtrate was concentrated under vacuum, and the residue was purified by silica gel column chromatography to give 1.15 g of yellow solid 2, with a yield of 62%. 1 H NMR (400MHz, CDCl3): δ=7.24-7.22(m,2H),7.13-7.09(m,6H),6.75(dd,J1=2.4,J2=8.4,2H),6.61(d,J=7.2,2H),6.54-6.53(m,2H),3.76(s,6H)ppm. 13C10 NMR (100MHz, CDCl3): δ=198.95, 159.23, 142.68, 140.43, 137.64, 136.55, 131.88, 129.72, 129.29, 126.97, 121.49, 114.85, 113.24, 55.40ppm. High-resolution mass spectrometry, ESI source, positive ion mode, molecular formula C10. 27 H 20 Cl2NaO3, theoretical values ​​485.0682, 486.0715, 487.0652, measured values ​​485.0676, 486.0711, 487.0657.

[0046]

[0047] Synthesis of Compound 3: Compound 2 (11.55 g) was added to 100 mL of methanesulfonic acid and stirred at 60 °C for 12 hours. The reaction mixture was poured into ice water, extracted with CH2Cl2, washed with saturated sodium bicarbonate aqueous solution and brine, dried over MgSO4, and concentrated under reduced pressure to give the crude product. The crude product was then recrystallized in CH2Cl2 to give white solid 3 with a mass of 9.10 g, yielding 82%. 1 H NMR (400MHz, CDCl3): δ = 7.75 (d, J = 1.6, 2H), 7.30 (d, J = 2.4, 2H), 7.07 (dd, J 1=2.0, J2=8.0,2H),6.72-6.70(m,2H),6.64-6.61(m,4H),3.88(s,6H)ppm. 13 CNMR (100MHz, CDCl3): δ=160.19, 147.73, 143.38, 141.85, 140.66, 133.90, 128.02, 125.10, 124.89, 120.41, 115.08, 105.46, 64.03, 55.73ppm. High-resolution mass spectrometry, ESI source, positive ion mode, molecular formula C 27 H 19 ClO3, theoretical values ​​445.0757, 447.0727, 446.0790, measured values ​​445.0753, 447.0731, 446.0785.

[0048]

[0049] Synthesis of Compound 4: Under a nitrogen atmosphere, Pd2(dba)3 (457.5 mg), S-phos (615.8 mg), t-BuONa (3.84 g), Compound 3 (4.44 g), 4,4′-dimethyldiphenylamine (4.14 g), and toluene (30 mL) were added to a Schlenk tube equipped with a magnetic stirrer. The reaction mixture was heated and stirred at 120 °C for 24 hours. After the reaction mixture cooled to room temperature, it was diluted with 30 mL of CH2Cl2, filtered through a diatomaceous earth pad, and washed with 30 mL of CH2Cl2. The filtrate was concentrated under vacuum, and the residue was purified by silica gel column chromatography to give a white solid 4 with a mass of 6.44 g, in 84% yield. 1 H NMR (400MHz, CDCl3): δ = 7.46 (d, J = 2.4, 2H), 7.15 (d, J = 2.0, 2H), 7.09-7.03 (m, 16H), 6.79 (dd ,J1=2.4,J2=8.4,2H),6.70-6.65(m,4H),6.61(d,J=8.4,2H)),3.83(s,6H),2.33(s,12H)ppm. 13 C10 NMR (100MHz, CDCl3): δ=159.76,147.96,145.73,143.52,142.87,142.47,141.82,132.30,129.99,124.68,124.45,123.44,114.66,114.26,105.02,63.98,55.72,20.96ppm. High-resolution mass spectrometry, ESI source, positive ion mode, molecular formula C10. 55 H 47 N2O2, theoretical value 767.3632, measured value 767.3632.

[0050]

[0051] Synthesis of Compound 5: Compound 4 (6.13 g) was dissolved in CH2Cl2 (40 mL) and cooled to 0 °C. Boron tribromide (3.10 mL) was then added dropwise to the solution at this temperature. The reaction mixture was heated to room temperature and stirred for 12 hours. After the reaction was complete, the mixture was cooled to 0 °C and quenched with cold water (50 mL). The organic layer was separated and washed with saturated sodium bicarbonate aqueous solution and brine, respectively. The combined organic extract was dried over sodium sulfate and concentrated under reduced pressure. Subsequently, the concentrated organic phase was dissolved in CH2Cl2 (40 mL), Et3N (2.80 mL) was added, and the mixture was stirred at 0 °C for 30 minutes. Then, a solution of trifluoromethanesulfonic anhydride (4.00 mL) in CH2Cl2 (24 mL) was added to the mixture, and the mixture was heated to room temperature and stirred for 12 hours. After the reaction was complete, cold water was added, the organic layer was separated, the combined organic extracts were dried with sodium sulfate, concentrated under reduced pressure to obtain crude product, and then separated and purified by silica gel column chromatography to obtain white solid 5 with a mass of 6.17 g and a yield of 77%. 1 H NMR (400MHz, CDCl3): δ = 7.49 (d, J = 2.0, 2H), 7.45 (d, J = 1.6, 2H), 7.11 (d, J = 8.0, 8H), 7.05 (d, J = 8.0, 8H), 6.99 (d d,J1=8.4,J2=2.4,2H),6.88(dd,J1=8.4,J2=2.0,2H),6.80(d,J=8.0,2H),6.62(d,J=8.4,2H),2.35(s,12H)ppm. 13 C NMR (100MHz, CDCl3): δ=149.45,148.90,148.65,145.17,143.99,140.85,140.67,132.97,130.08,125. 37,124.79,122.02(q,J=342.0Hz),117.12,114.09(d,J=4.0Hz),113.37(d,J=4.0Hz),64.18,20.85ppm. 19 FNMR (376MHz, CDCl3): δ=72.92ppm. High-resolution mass spectrometry, ESI source, positive ion mode, molecular formula C 55 H 44 F6N2O6S2, theoretical value 1003.2305, test value 1003.2306.

[0052]

[0053] Synthesis of compound T02: Under a nitrogen atmosphere, Pd2(dba)3 (137.3 mg), Xantphos (260.4 mg), t-BuONa (1.15 g), compound 5 (3.00 g), 4,4′-dimethyldiphenylamine (1.24 g), and toluene (10 mL) were added to a Schlenk tube equipped with a magnetic stirrer. The reaction mixture was heated and stirred at 120 °C for 24 hours. After the reaction mixture cooled to room temperature, it was diluted with CH2Cl2, filtered through a diatomaceous earth filter, and washed with CH2Cl2. The filtrate was concentrated under vacuum, and the residue was purified by silica gel column chromatography to give a white solid T02 with a mass of 2.47 g and a yield of 75%. 1 H NMR (400MHz, CDCl3): δ = 7.37 (d, J = 2.0, 4H), 7.07-6.99 (m, 32H), 6.82 (dd, J1 = 8.0, J2 = 2.0, 4H), 6.69 (d, J = 8.0, 4H), 2.32 (s, 24H) ppm. 13 C10 NMR (100MHz, CDCl3): δ=147.88,145.79,143.68,142.62,132.10,129.98,124.68,124.14,124.04,115.55,64.32,20.93ppm. High-resolution mass spectrometry, ESI source, positive ion mode, molecular formula C10. 81 H 69 N4, theoretical value 1097.5517, test value 1097.5509.

[0054] Application Example 1

[0055] Phosphorescent organic electroluminescent devices were prepared according to the following method:

[0056] 1. Cleaning ITO (Indium Tin Oxide) Glass: Wash with alkali and deionized water in sequence, dry in a vacuum drying oven, and then treat in a plasma cleaner for 10 minutes;

[0057] 2. A hole injection layer HAT-CN (10nm), a hole transport layer TAPC or TO2 (25nm), and an electron blocking layer TCTA (10nm) are sequentially vacuum-deposited on the anode ITO glass at a deposition rate of 0.1nm / s.

[0058] 3. A light-emitting layer is vacuum-deposited on top of the electron blocking layer, with CBP or mCBP as the main material and doped with FIrPic / Ir(mphmp)2tmd / Ir(ppy)2acac / BCz-BN, at a deposition rate of 0.1 nm / s and a deposition thickness of 10 nm or 20 nm.

[0059] 4. Vacuum evaporation of an electron transport layer TmPyPb (40nm) on top of the luminescent layer at a deposition rate of 0.1nm / s; 5. Vacuum evaporation of an electron injection layer LiF (0.8nm) on top of the electron transport layer at a deposition rate of 0.08nm / s; 6. Vacuum evaporation of a cathode Al (100nm) on top of the electron injection layer at a deposition rate of 0.1nm / s.

[0060] The device structures used include:

[0061] Red light: ITO / HAT-CN (10nm) / T02 (25nm) / TCTA (10nm) / CBP: 1wt%

[0062] Ir(mphmp)2tmd(10nm) / TmPyPB(50nm) / LiF(0.8nm) / Al(100nm);

[0063] ITO / HAT-CN(10nm) / TAPC(25nm) / TCTA(10nm) / CBP:1wt%Ir(mphmp)2tmd(10nm) / TmPyPB(50nm) / LiF(0.8nm) / Al(100nm);

[0064] Green light: ITO / TO2 (30nm) / TCTA (10nm) / CBP: 10wt% Ir(ppy)2acac(20

[0065] nm) / TmPyPB(40nm) / LiF(0.8nm) / Al(100nm);

[0066] ITO / TAPC(30nm) / TCTA(10nm) / CBP:10wt%Ir(ppy)2acac(20nm) / TmPyPB(40nm) / LiF(0.8nm) / Al(100nm);

[0067] Blue light: ITO / TO2 (30nm) / TCTA (10nm) / mCBP: 15wt% FIrPic (23nm) / TmPyPB (40nm) / LiF (0.8nm) / Al (100nm);

[0068] ITO / TAPC(30nm) / TCTA(10nm) / mCBP:15wt%FIrPic(23nm) / TmPyPB(40nm) / LiF(0.8nm) / Al(100nm);

[0069] BN-MR: ITO / T02(30nm) / TCTA(10nm) / mCBP:15wt%FIrPic:0.5wt%BCz-BN(23nm) / TmPyPB(40nm) / LiF(0.8nm) / Al(100nm);

[0070] ITO / TAPC(30nm) / TCTA(10nm) / mCBP:15wt%FIrPic:0.5wt%BCz-BN(23nm) / TmPyPB(40nm) / LiF(0.8nm) / Al(100nm).

[0071] The performance test results of devices one through eight prepared using Examples 1-8 are shown in Table I.

[0072] Table I

[0073] Device Number Hole transport materials Power efficiency (lm / W) <![CDATA[EQE max (%)]]> Device 1 T02 46.3 26.1 Device 2 TAPC 44.9 25.1 Device 3 T02 97.6 26.4 Device 4 TAPC 92.6 25.4 Device 5 T02 52.6 25.4 Device Six TAPC 51.5 24.8 Component 7 T02 53.4 29.8 Device 8 TAPC 50.5 28.7

[0074] For comparison, the classic TAPC hole transport material was used as a reference in the fabrication of this invention. As shown in Table I, the organic electroluminescent device fabricated based on the material of this invention exhibits better device performance, with a maximum current efficiency of 97.6 lm / W and a maximum EQE of 29.8%. Compared to the TAPC device, it demonstrates superior characteristics in terms of current efficiency and device efficiency.

[0075] The above descriptions are merely some embodiments of the present invention and are not intended to limit the present invention. Any modifications or substitutions made within the spirit and principles of the present invention are included within the scope of protection of the present invention.

Claims

1. A series of 3,3',6,6'-tetrasubstituted spirodifluorene derivatives, used as hole transport materials or host materials in organic electroluminescent devices, or as hole transport materials in perovskite solar cells in organic photoelectric conversion devices, characterized in that, Its structural features are shown in Equation I: Ar is selected from aryl groups with 6 to 30 carbon atoms, whether substituted or unsubstituted, and heteroaryl groups with 6 to 30 carbon atoms, wherein the heteroatoms of the heteroaryl group are preferably selected from oxygen, nitrogen, sulfur, and selenium atoms, and the substituents include, but are not limited to, hydrogen, deuterium, halogen, trifluoromethyl, C1-50 alkanes, alkoxy, alkylsilyl, nitro, cyano, amino, substituted amino, ester, aryl, heteroaryl, and aldehyde groups.

2. The 3,3',6,6'-tetrasubstituted spirodifluorene derivative as described in claim 1, characterized in that, The spirodifluorene derivative is selected from the following structures:

3. The organic electroluminescent device prepared according to claim 1 or 2, characterized in that, The structure of the hole transport material and the host material in the organic electroluminescent device can be the 3,3',6,6'-tetrasubstituted spirodifluorene derivative as described in any one of claims 1 and 2.

4. The organic photoelectric conversion device prepared according to claim 1 or 2, characterized in that, The structure of the hole transport material in the organic photoelectric conversion device comprising the perovskite solar cell can be the 3,3',6,6'-tetrasubstituted spirodifluorene derivative as described in any one of claims 1 and 2.

5. The method for preparing the 3,3',6,6'-tetrasubstituted spirodifluorene derivative as described in claim 1 or 2, characterized in that, Rapid construction of 3,3',6,6'-tetrasubstituted spirodifluorene structures using transition metal-catalyzed ortho-hydrocarbon arylation reactions or Suzuki coupling reactions.

Images