Aryl silicon modified fluorene organic photoelectric functional material and synthesis method thereof
By introducing aryl silicon into fluorene derivatives, the problem of 4-position substitution synthesis is solved, and the efficient synthesis of fluorene organic photoelectric materials with excellent photoelectric properties is achieved.
Patent Information
- Application Number
- CN202510172803.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-17
- Publication Date
- 2025-05-30
AI Technical Summary
The difficulty of synthesis of fluorene derivatives in 4-position substitution is greatly increased, and after the introduction of aryl silicon, there are challenges in maintaining the triplet energy level while regulating thermal stability and photoelectric transmission performance.
By using ortho-dibromoylbenzene as the starting material, 4-bromoylfluorene derivatives are efficiently synthesized through lithiation and ring-closing reactions, and Suzuki reactions are carried out with aryl silicon boroate to synthesize aryl silicon-modified fluorene organic photoelectric materials.
The fluorene-based organic photoelectric materials modified by aryl silicon have been achieved efficiently, maintain a high triplet energy level, improve thermal stability and photoelectric transmission performance, and are suitable for high-efficiency electroluminescent devices.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic optoelectronic functional materials, and particularly relates to a fluorene-based organic optoelectronic functional material modified by arylsilicon and a synthesis method thereof. Background Art
[0002] Organic electroluminescent display technology has the advantages of low-voltage driving, high brightness, high efficiency, and the ability to achieve large-area color display. It is a research hotspot internationally in recent years and has become the leader in the future lighting and display fields. Fluorene derivatives have a relatively high triplet state and a relatively high fluorescence quantum yield. They are widely used as host materials in blue, green and other electroluminescent devices. Moreover, the carbons at the 2, 7, and 9 positions have relatively high activity and are easily substituted by substituents, showing high chemical modifiability.
[0003] Due to the relatively high reactivity of the 2- and 7-positions of the fluorene ring, the selectivity at the 4-position is often poor. At the same time, the steric hindrance at the 4-position is relatively large, greatly increasing the synthesis difficulty of 4-substituted fluorene compounds. Meanwhile, introducing arylsilicon at the 4-position of the fluorene ring aims to maintain the triplet energy level of the host material while adjusting its thermal stability and optoelectronic transport properties. At the same time, the tetrahedral configuration of the silicon atom can effectively prevent intermolecular interactions in the solid film, thereby forming a uniform and smooth amorphous film, and thus realizing a highly efficient electroluminescent device.
[0004] In the present invention, the fluorene-based organic optoelectronic material modified by arylsilicon uses o-dibromobenzene as the starting material, and through lithiation reaction and cyclization reaction, 4-bromofluorene derivatives are efficiently synthesized, and then Suzuki reaction is carried out with arylsilicon borate ester to synthesize a series of fluorene-based organic optoelectronic materials modified by arylsilicon. Meanwhile, this series of compounds have relatively high triplet energy levels, glass transition temperatures and thermal decomposition temperatures, and can be used as host materials in organic electroluminescent devices. At present, there are no relevant literature and patent reports on this target compound and its synthesis method. Summary of the Invention
[0005] The present invention provides a fluorene-based organic optoelectronic functional material modified by arylsilicon and a synthesis method thereof. The method of the present invention has the advantages of cheap and easily available raw materials, convenient production, environmental protection and safety, and easy purification.
[0006] To achieve the above technical purpose, the technical solution of the present invention is as follows:
[0007] A fluorene-based organic optoelectronic functional material modified by arylsilicon, and its structural formula is as follows:
[0008]
[0009] Wherein, R1 and R2 are respectively one of the following substituents:
[0010]
[0011] R1 and R2 can be the same or different simultaneously.
[0012] Among them, the aryl-silicon modified fluorene-based organic optoelectronic functional materials are selected from the compounds with the following structural formula:
[0013]
[0014] The present invention also provides a synthesis method of the fluorene-based organic optoelectronic functional materials, and the reaction formula is as follows:
[0015]
[0016] Among them, the target compound is synthesized through the following steps:
[0017] (1) Synthesis of intermediate II: Under an argon atmosphere, add o-dibromobenzene, m-xylene and methyltetrahydrofuran to the reaction kettle, cool down to -78 °C, slowly drop in n-butyllithium, stir, slowly drop in compound I, raise the temperature to room temperature, and react overnight; stop the reaction, drop in dilute hydrochloric acid to quench the reaction, extract, concentrate the solvent under reduced pressure, and purify by column chromatography to obtain an alcohol intermediate. Add the alcohol intermediate and dichloromethane to the reaction kettle, cool down to 0 °C, and add AlCl 3 Or react glacial acetic acid and concentrated hydrochloric acid. After the reaction is completed, pour the reaction solution into ice water, extract, concentrate the solvent under reduced pressure, and purify by column chromatography to obtain a off-white powder 4-bromofluorene derivative compound II;
[0018] (2) Synthesis of the target compound: Under an argon atmosphere, add compound II, compound III, dichlorobis(tert-butyl)-(4-dimethylaminophenyl)phosphine palladium(II) and potassium carbonate to the reaction kettle, and use toluene, methanol and water as a mixed solvent, heat to reflux, and react for 12 h; after the reaction is completed, add dichloromethane for extraction, wash the organic phase with water, separate out the organic phase, concentrate the solvent under reduced pressure, and purify by column chromatography to obtain the target compound.
[0019] Among them, in step (1), the molar ratio of o-dibromobenzene to n-butyllithium is 1.0:0.8 - 1.2, preferably 1.0:1.0; the molar ratio of o-dibromobenzene to compound I is 1:1.5 - 2.5, preferably 1:2.
[0020] Among them, in step (1), the volume ratio of m-xylene to methyltetrahydrofuran is 2.0 - 5.0:1.0, preferably the volume ratio is 3.0:1.0.
[0021] Among them, in step (2), the molar ratio of compound II to compound III is 1:0.8 - 1.2, preferably 1:1; the molar ratio of compound II to dichloro-di-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) is 1:0.1% - 0.5%; the molar ratio of compound II to potassium carbonate is 1:1.5 - 2.5, preferably 1:2; the volume ratio of toluene, methanol and water is 2.0 - 5.0:0.1 - 1.0:1.0 - 3.0, preferably the volume ratio of 3:0.5:2.5.
[0022] Compared with the prior art, the present invention has the following beneficial effects:
[0023] (1) Due to the high reactivity of the 2-position and 7-position of the fluorene ring, the selectivity of the 4-position is often poor, and at the same time, the steric hindrance at the 4-position is large, which greatly increases the synthesis difficulty of 4-substituted fluorene compounds. The present invention uses o-dibromobenzene as the starting material, and through lithiation reaction and ring-closing reaction, 4-bromo-fluorene derivatives are efficiently synthesized. At the same time, the raw materials of this process are cheap and easy to obtain, and the production cycle is short, which significantly reduces the production cost of this product and is suitable for industrial production applications.
[0024] (2) Using fluorene as the core skeleton, introducing tetraphenylsilane at the 4-position can adjust its thermal stability and optoelectronic transport properties while maintaining the triplet energy level of the host material; at the same time, the tetrahedral configuration of silicon atoms can effectively prevent intermolecular interactions in the solid film, thereby forming a uniform and smooth amorphous film, thus realizing a highly efficient electroluminescent device. Specific embodiments
[0025] The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.
[0026] Example 1:
[0027] This example provides a synthesis method of an aryl-silicon-modified fluorene-based organic optoelectronic functional material, and the reaction formula is as follows:
[0028]
[0029] The synthesis method includes the following steps:
[0030] (1) Synthesis of 4-bromo-9,9-dimethyl-9H-fluorene
[0031] Under argon protection, o-dibromobenzene (11.8 g), m-xylene 120 mL and methyltetrahydrofuran 40 mL were added to a reaction kettle, the temperature was lowered to -78 °C, n-butyllithium (30 mL, 1.6 mol / L) was dropped in, stirred, and then acetone (0.9 g) was dropped in. The temperature was raised to room temperature and the reaction was carried out overnight; the reaction was stopped, dilute hydrochloric acid was dropped in to quench the reaction, extracted with dichloromethane, the organic phases were combined, the solvent was concentrated under reduced pressure, and the alcohol intermediate was purified by column chromatography. The alcohol intermediate was added to a reaction kettle, 100 mL of dichloromethane was used as a solvent, the temperature was lowered to 0 °C, and AlCl 3 (0.7 g) was added, the reaction was stopped, the reaction solution was poured into ice water, extracted three times with dichloromethane, the organic phases were combined, the solvent was concentrated under reduced pressure, and 10.6 g of a white solid was obtained by column chromatography purification, with a yield of 76.8% and a content of 99.6%.).
[0032] (2) Synthesis of Compound 1
[0033] Under argon protection, 4-bromo-9,9-dimethyl-9H-fluorene (2.7 g), Compound III (4.6 g), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (13.8 mg), K 2 CO 3 (2.7 g) were added to a reaction kettle, and toluene (60 mL), methanol (7.5 mL) and water (30 mL) were used as a mixed solvent, and the reaction was heated under reflux for 12 h. The reaction was stopped, extracted three times with dichloromethane, the organic phase was washed with water, the organic phases were combined, the solvent was concentrated under reduced pressure, and 4.3 g of a white solid powder was obtained by column chromatography purification, with a yield of 80.6% and a content of 99.8%.
[0034] ESI, m / z: [M+H] + calcd for C 39 H 32 Si, theoretical value: 528.23, measured value: 528.16.
[0035] Characterization data of Compound 1: 1 H NMR (500 MHz, CDCl 3)δ 7.77 (t, J = 1.6 Hz, 1H), 7.66 (dt, J = 7.2, 1.6 Hz, 1H), 7.62 (dt, J = 6.8, 1.6 Hz, 6H), 7.57 (dt, J = 7.6, 1.6 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.44–7.40 (m, 5H), 7.38–7.34 (m, 6H), 7.32 (t, J = 7.6 Hz, 1H), 7.24 (td, J = 7.6, 1.2 Hz, 1H), 7.16 (dd, J = 7.6, 1.2 Hz, 1H), 6.99 (td, J = 7.6, 1.2 Hz, 1H), 6.95–6.93 (m, 1H), 1.54–1.49 (m, 6H).
[0036] 13 C NMR (126 MHz, CDCl 3 ) δ 154.41, 154.13, 140.91, 139.12, 138.00, 136.86, 136.59, 136.40, 135.73, 134.68, 134.25, 130.66, 129.73, 129.10, 128.14, 128.03, 127.00, 126.76, 126.57, 123.17, 122.44, 121.64, 46.37.
[0037] Example 2:
[0038] This example provides a synthesis method for an aryl-silicon modified fluorene-based organic optoelectronic functional material, and the reaction formula is as follows:
[0039]
[0040] The synthesis method includes the following steps:
[0041] (1) Synthesis of 4-bromo-9-methyl-9-phenyl-9H-fluorene
[0042] Under argon protection, o-dibromobenzene (11.8 g), m-xylene 120 mL, and methyltetrahydrofuran 60 mL were added to the reaction kettle, cooled to -78 °C, n-butyllithium (25 mL, 1.6 mol / L) was slowly added dropwise, stirred at low temperature for 30 min, and then acetophenone (3.9 g) was slowly added dropwise, and the temperature was raised to room temperature, and the reaction was carried out overnight; the reaction was stopped, dilute hydrochloric acid was added dropwise to quench the reaction, extracted, the organic phases were combined, the solvent was concentrated under reduced pressure, and the alcohol intermediate was purified by column chromatography. The alcohol intermediate was added to the reaction kettle, and then dichloromethane 100 mL was added, cooled to -0 °C, and AlCl was added in batches 3(0.7 g), The reaction was stopped, and the reaction solution was poured into ice water. It was extracted with dichloromethane (100 mL×3), the solvent was concentrated under reduced pressure, and a white solid powder of 6.9 g was obtained by column chromatography purification, with a yield of 82.4% and a content of 99.5%.
[0043] (2) Synthesis of Compound 2
[0044] Under argon protection, 4-bromo-9-methyl-9-phenyl-9H-fluorene (3.4 g), Compound III (4.5 g), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (4.2 mg) and K 2 CO 3 (2.5 g) were added to the reaction kettle. Toluene (60 mL), methanol (30 mL) and water (90 mL) were used as the mixed solvent. It was heated to reflux and reacted for 12 h. The reaction was stopped, extracted with dichloromethane (100 mL×3), the organic phase was washed with water, the organic phases were combined, the solvent was concentrated under reduced pressure, and a white solid powder of 5.1 g was obtained by column chromatography purification, with a yield of 86.2% and a content of 99.6%.
[0045] ESI, m / z: [M+H] + calcd for C 44 H 34 Si, Theoretical value: 590.24, Measured value: 590.09.
[0046] Characterization data of Compound 2: 1 HNMR(500 MHz, CDCl 3 ) δ 7.79 (t, J = 1.6 Hz, 1H), 7.68 (d, J = 7.6 Hz, 1H), 7.64–7.59 (m, 7H), 7.53 (t, J = 7.6 Hz, 1H), 7.44–7.40 (m, 3H), 7.36 (t, J = 7.2 Hz, 6H), 7.25–7.14 (m, 10H), 6.98 (d, J = 3.2 Hz, 2H), 1.93–1.87 (m, 3H).
[0047] 13 C NMR(126 MHz, CDCl 3 ) δ 140.75, 136.88, 136.60, 135.78, 134.23, 130.47, 129.76, 129.27, 128.42, 128.22, 128.05, 127.45, 127.20, 126.76, 126.71, 126.45, 124.04, 123.24, 54.29, 25.60.
[0048] Example 3:
[0049] This embodiment provides a synthesis method of an aryl-silicon-modified fluorene-based organic optoelectronic functional material, and the reaction formula is as follows:
[0050]
[0051] The synthesis method includes the following steps:
[0052] (1) Synthesis of 4-bromo-9,9-diphenyl-9H-fluorene
[0053] Under argon protection, o-dibromobenzene (11.8 g), m-xylene 120 mL, and methyltetrahydrofuran 24 mL were added to a reaction kettle, cooled to -78 °C, n-butyllithium (37.5 mL, 1.6 mol / L) was slowly dropped in, stirred at low temperature for 30 min, then benzophenone (3.6 g) was slowly dropped in, and the temperature was raised to room temperature, and the reaction was carried out overnight; the reaction was stopped, dilute hydrochloric acid was dropped in to quench the reaction, extracted, the organic phases were combined, the solvent was concentrated under reduced pressure, and the alcohol intermediate was purified by column chromatography. The alcohol intermediate was added to the reaction kettle, then 30 mL of glacial acetic acid was added, heated to reflux, a few drops of concentrated hydrochloric acid were added, reacted for 8 h, the reaction was stopped, cooled to room temperature, and a white powder 7.8 g was obtained by column chromatography, with a yield of 78.5% and a content of 99.6% (HPLC).
[0054] (2) Synthesis of Compound 3
[0055] Under argon protection, 4-bromo-9,9-diphenyl-9H-fluorene (4.0 g), Compound III (4.6 g), dichloroditert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (28.5 mg), and K 2 CO 3 (2.8 g) were added to a reaction kettle, toluene (60 mL), methanol (1.2 mL), and water (12 mL) were used as a mixed solvent, heated to reflux, and reacted for 12 h. The reaction was stopped, extracted with dichloromethane, the organic phase was washed with water, the organic phases were combined, the solvent was concentrated under reduced pressure, and a white solid powder 5.3 g was purified by column chromatography, with a yield of 81.8% and a content of 99.8%. ESI, m / z: [M+H] + calcd for C 49 H 36 Si, theoretical value: 652.26, measured value: 652.16.
[0056] Characterization data of Compound 3: 1 H NMR (500 MHz, CDCl 3)δ 7.78 (s, 1H), 7.70 (d, J = 7.2 Hz, 1H), 7.67–7.59 (m, 7H), 7.54 (t, J = 7.6 Hz, 1H), 7.46–7.35 (m, 11H), 7.28–7.16 (m, 13H), 7.02–6.95 (m, 2H).
[0057] 13 C NMR (126 MHz, CDCl 3 )δ 146.23, 140.64, 137.12, 136.58, 135.81, 134.77, 134.19, 130.59, 129.76, 129.59, 128.44, 128.32, 128.23, 128.05, 127.44, 127.17, 127.02, 126.75, 126.19, 125.33, 123.40, 65.19.
[0058] Example 4:
[0059] This example provides a method for synthesizing an aryl-silicon modified fluorene-based organic optoelectronic functional material, and the reaction formula is as follows:
[0060]
[0061] The synthesis method includes the following steps:
[0062] (1) Synthesis of 4-bromo-9-(4-(tert-butyl)phenyl)-9-phenyl-9H-fluorene
[0063] Under argon protection, o-dibromobenzene (11.8 g), m-xylene 120 mL and methyltetrahydrofuran 40 mL were added to the reaction kettle, cooled to -78 °C, n-butyllithium (30 mL, 1.6 mol / L) was slowly added dropwise, stirred at low temperature for 30 min, and then 4-tert-butylbenzophenone (6.7 g) was slowly added dropwise, and the temperature was raised to room temperature, and the reaction was carried out overnight; the reaction was stopped, dilute hydrochloric acid was added dropwise to quench the reaction, extracted, the organic phases were combined, the solvent was concentrated under reduced pressure, and the alcohol intermediate was purified by column chromatography. The alcohol intermediate was added to the reaction kettle, then 30 mL of glacial acetic acid was added, heated to reflux, a few drops of concentrated hydrochloric acid were added, and the reaction was carried out for 8 h. The reaction was stopped, cooled to room temperature, and a white powder of 8.5 g was obtained by column chromatography purification, with a yield of 74.8% and a content of 99.4% (HPLC).
[0064] (2) Synthesis of Compound 4
[0065] Under argon protection, 4-bromo-9-(4-(tert-butyl)phenyl)-9-phenyl-9H-fluorene (4.5 g), Compound III (3.4 g), dichlorobis(tert-butyl)-(4-dimethylaminophenyl)phosphine palladium(II) (5.6 mg) and K 2 CO 3 (2.0 g) were added to a reaction kettle. Toluene (60 mL), methanol (10 mL) and water (15 mL) were used as a mixed solvent, and the mixture was heated under reflux for 12 h. The reaction was stopped, and the mixture was extracted with dichloromethane. The organic phase was washed with water, and the organic phases were combined and concentrated under reduced pressure. The residue was purified by column chromatography to obtain 6.2 g of a white solid powder with a yield of 86.9% and a content of 99.9%. ESI, m / z: [M+H] + calcd for C 53 H 44 Si, theoretical value: 708.32, measured value: 708.24.
[0066] Characterization data of Compound 4: 1 HNMR(500 MHz, CDCl 3 ) δ 7.69 (d, J = 5.2 Hz, 1H), 7.59 (d, J = 7.2 Hz, 1H), 7.57–7.48 (m, 7H), 7.43 (t, J = 7.6 Hz, 1H), 7.37–7.24 (m, 11H), 7.18–7.02 (m, 12H), 6.92–6.85 (m, 2H), 1.20 (s, 9H).
[0067] 13 C NMR(126 MHz, CDCl 3 ) δ 152.42, 146.45, 142.88, 140.70, 137.11, 136.59, 135.78, 134.76, 134.21, 130.62, 129.75, 129.50, 128.46, 128.25, 128.21, 128.05, 127.36, 127.09, 126.93, 126.65, 126.23, 125.39, 125.19, 123.35, 64.81, 34.48, 31.48. Example 5:
[0068] This example provides a method for synthesizing an aryl-silicon-modified fluorene-based organic optoelectronic functional material, and the reaction formula is as follows:
[0069]
[0070] The synthesis method includes the following steps:
[0071] (1) Synthesis of 4-bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene
[0072] Under argon protection, o-dibromobenzene (11.8 g), m-xylene 120 mL and methyltetrahydrofuran 40 mL were added to a reaction kettle, the temperature was lowered to -78 °C, n-butyllithium (30 mL, 1.6 mol / L) was slowly added dropwise, and the mixture was stirred at low temperature for 30 min. Then, bis(4-tert-butylphenyl)methanone (9.1 g) was slowly added dropwise, the temperature was raised to room temperature, and the reaction was carried out overnight; the reaction was stopped, dilute hydrochloric acid was added dropwise to quench the reaction, extraction was carried out, the organic phases were combined, the solvent was concentrated under reduced pressure, and the alcohol intermediate was purified by column chromatography. The alcohol intermediate was added to the reaction kettle, and then acetic acid 30 mL was added. The mixture was heated to reflux, a few drops of concentrated hydrochloric acid were added, and the reaction was carried out for 8 h. The reaction was stopped, cooled to room temperature, and a white powder 9.8 g was obtained by column chromatography purification, with a yield of 75.5% and a content of 99.4%.
[0073] (2) Synthesis of Compound 5
[0074] Under argon protection, 4-bromo-9,9-bis(4-(tert-butyl)phenyl)-9H-fluorene (5.1 g), Compound III (4.2 g), dichlorobis(tert-butyl)-(4-dimethylaminophenyl)phosphine palladium(II) (17.0 mg) and K 2 CO 3 (2.3 g) were added to a reaction kettle. Toluene (60 mL), methanol (15 mL) and water (37.5 mL) were used as a mixed solvent, and the mixture was heated to reflux and reacted for 12 h. The reaction was stopped, and extraction was carried out with dichloromethane (100 mL×3). The organic phase was washed with water, the organic phases were combined, the solvent was concentrated under reduced pressure, and a white solid powder 6.6 g was obtained by column chromatography purification, with a yield of 86.9% and a content of 99.8%. ESI, m / z: [M+H] + calcd for C 57 H 52 Si, theoretical value: 764.38, measured value: 764.24.
[0075] Characterization data of Compound 5: 1 HNMR(400MHz,CDCl 3 )δ7.75(d,J=1.6Hz,1H),7.66(dt,J=7.2,1.6Hz,1H),7.63–7.54(m,7H),7.51(t,J=7.6Hz,1H),7.45–7.33(m,11H),7.22(q,J=9.6,8.8Hz,5H),7.18–7.08(m,6H),6.95(dtd,J=16.0,8.0,1.2Hz,2H),1.27(d,J=2.8Hz,18H).
[0076] 1313C NMR (101 MHz, CDCl 3 ) δ 149.25, 149.20, 143.13, 140.75, 138.01, 137.07, 136.58, 135.76, 134.18, 130.64, 129.75, 129.42, 128.20, 128.05, 128.03, 127.29, 127.01, 126.85, 126.28, 125.45, 125.13, 123.28, 34.46, 31.50.
[0077] Application Example 1 Preparation of Organic Electroluminescent Device
[0078] An OLED device was prepared using Compound 5 in the examples of the present invention as the host material.
[0079] The device structure used was ITO / HATCN (5 nm) / TAPC (30 nm) / Ir(ppy) 3 : Compound 5 (10 wt%) (20 nm) / TPBi (40 nm) / LiF (0.9 nm) / Al (100 nm). Among them, HATCN and TAPC were used as the hole injection layer (HIL) and hole transport layer (HTL) respectively; TPBi and LiF were the electron transport layer (ETL) and electron injection layer (EIL) respectively;
[0080] Comparative Example 1:
[0081] The device structure used was ITO / HATCN (5 nm) / TAPC (30 nm) / Ir(ppy) 3 : mCP (10 wt%) (20 nm) / TPBi (40 nm) / LiF (0.9 nm) / Al (100 nm). Among them, HATCN and TAPC were used as the hole injection layer (HIL) and hole transport layer (HTL) respectively; TPBi and LiF were the electron transport layer (ETL) and electron injection layer (EIL) respectively;
[0082] The structural formula of the compound in the device is as follows:
[0083]
[0084] The test results of the luminescence characteristics of the organic electroluminescent devices prepared in Application Example 1 of the present invention and Comparative Example 1 are shown in Table 1.
[0085]
[0086] It can be seen that when the arylsilicon-modified fluorene derivatives of the present invention are applied to an organic electroluminescent device, the organic electroluminescent device exhibits a lower driving voltage, a higher luminous efficiency, a longer service life, and better durability and reliability.
[0087] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. An aromatic silicon-modified fluorene organic photoelectric functional material, characterized in that The structural formula is as follows: Wherein, R1 and R2 are respectively one of the following substituents: R1 and R2 may be the same or different.
2. The aryl silicon modified fluorene organic photoelectric functional material according to claim 1, characterized in that Selected from compounds with the following structural formula:
3. A method for synthesizing the fluorene organic photoelectric functional material according to claim 1 or 2, characterized in that The reaction formula is as follows: The target compound is synthesized by the following steps: (1) Synthesis of intermediate II: Under an argon atmosphere, o-dibromobenzene, m-xylene and methyltetrahydrofuran are added to a reaction kettle, the temperature is lowered to -78°C, n-butyl lithium is slowly added dropwise, stirred, compound I is slowly added, the temperature is raised to room temperature, and the reaction is allowed to proceed overnight; the reaction is stopped, dilute hydrochloric acid is added dropwise to quench the reaction, extraction is performed, the solvent is concentrated under reduced pressure, and the alcohol intermediate is obtained by purification by column chromatography; the alcohol intermediate and dichloromethane are added to a reaction kettle, the temperature is lowered to 0°C, AlCl3 or glacial acetic acid and concentrated hydrochloric acid are added in batches to react, and after the reaction is completed, the reaction solution is poured into ice water, extraction is performed, the solvent is concentrated under reduced pressure, and purification is performed by column chromatography to obtain an off-white powder 4-bromofluorene derivative compound II; (2) Synthesis of the target compound: Under an argon atmosphere, compound II, compound III, dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) and potassium carbonate were added to a reaction kettle, and toluene, methanol and water were used as a mixed solvent. The mixture was heated to reflux and reacted for 12 hours. After the reaction was completed, dichloromethane was added to extract and the organic phase was washed with water. The organic phase was separated and concentrated under reduced pressure. The target compound was purified by column chromatography.
4. The method for synthesizing a fluorene-based organic photoelectric functional material according to claim 3, characterized in that: In step (1), the molar ratio of o-dibromobenzene to n-butyllithium is 1.0:0.8-1.2; the molar ratio of o-dibromobenzene to compound I is 1.5-2.5:1.
0.
5. The method for synthesizing a fluorene-based organic photoelectric functional material according to claim 3, characterized in that: In step (1), the volume ratio of m-xylene to methyltetrahydrofuran is 2.0-5.0:1.
0.
6. The method for synthesizing a fluorene-based organic photoelectric functional material according to claim 3, characterized in that: In step (2), the molar ratio of compound II to compound III is 1:0.8-1.2; the molar ratio of compound II to dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) is 1:0.05%-0.5%; the molar ratio of compound II to potassium carbonate is 1:1.5-2.5; the volume ratio of toluene, methanol and water is 2.0-5.0:0.1-1.0:1.0-3.0.