Aryl silicon modified spiro organic photoelectric functional material and synthesis method thereof
By using the lithiation reaction and Suzuki reaction methods in the synthesis of spirofluorene derivatives, aryl silicon modified spirocyclic organic photoelectric functional materials were successfully synthesized, solving the challenges of synthesis difficulty and performance adjustment, and achieving high-efficiency electroluminescent device performance.
Patent Information
- Application Number
- CN202510172802.9
- 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 prior art encounters the problems of poor selectivity and difficult synthesis when synthesizing 4-position substituted spirofluorene derivatives. At the same time, while maintaining the triplet energy level, it also has the challenge of adjusting its thermal stability and photoelectric transmission performance.
By using orthodimbenzene as the starting material, 4-bromospirofluorene derivatives are efficiently synthesized through lithiation and ring-closing reactions, and then Suzuki reactions are carried out with aryl silicon boroate to synthesize aryl silicon-modified spirocyclic organic photoelectric functional materials.
It realizes the efficient synthesis of aryl silicon modified screw ring organic photoelectric functional materials, maintains a high triplet energy level, improves thermal stability and photoelectric transmission performance, and is suitable for use in high-efficiency electroluminescent devices.
Smart Images
Figure BDA0005274538430000021 
Figure BDA0005274538430000022 
Figure BDA0005274538430000023
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic optoelectronic functional materials, and particularly relates to a spiro organic optoelectronic functional material modified by arylsilicon and a synthesis method thereof. Background Art
[0002] Organic light-emitting diodes have attracted much attention due to their broad development prospects and great potential application values in technical fields such as flat panel displays and solid state lighting. Compared with inorganic materials, organic light-emitting materials have many advantages that inorganic materials cannot match: light weight, low driving voltage, low energy consumption, high brightness, wide viewing angle, fast response speed, simple preparation process, and so on.
[0003] Fluorene derivatives have a relatively high triplet state and a relatively high fluorescence quantum yield, and are widely used as host materials in blue, green and other electroluminescent devices. Moreover, the carbon atoms at the 2, 7, and 9 positions have relatively high activity and are easily substituted by substituents, and have relatively high chemical modifiability.
[0004] Due to the relatively high reactivity of the 2- and 7-positions of fluorene, the selectivity at the 4-position is often poor. At the same time, the steric hindrance at the 4-position is relatively large, which greatly increases the synthesis difficulty of 4-substituted spirofluorene derivatives. At the same time, introducing arylsilicon at the 4-position of spirofluorene derivatives 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 silicon atoms can effectively prevent intermolecular interactions in the solid thin film, thereby forming a uniform and smooth amorphous thin film, so as to achieve a highly efficient electroluminescent device. In the present invention, the spiro organic optoelectronic functional material modified by arylsilicon uses o-dibromobenzene as the starting material, and through a lithiation reaction and a ring-closing reaction, 4-bromospirofluorene derivatives are efficiently synthesized, and then a Suzuki reaction is carried out with arylsilicon borate ester to synthesize a series of spiro organic optoelectronic functional materials modified by arylsilicon. At the same time, this series of compounds has 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, neither relevant literature nor patents have reported this target compound and its synthesis method. Summary of the Invention
[0005] The present invention provides a spiro 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] In order to achieve the above technical objectives, the technical solution of the present invention is as follows:
[0007] A spiro organic optoelectronic functional material modified by arylsilicon has the following structural formula:
[0008]
[0009] Among them, R is respectively one of the following substituents:
[0010]
[0011] They can be the same or different simultaneously.
[0012] Among them, the aryl-silicon-modified spiro organic optoelectronic functional materials are selected from the compounds with the following structural formulas:
[0013]
[0014] The present invention also provides a synthesis method of the spiro 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, add compound I in batches, raise the temperature to room temperature, and react overnight. After the reaction is completed, 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 to the reaction kettle, add glacial acetic acid and concentrated hydrochloric acid, heat to reflux for reaction, extract, concentrate the solvent under reduced pressure, and purify by column chromatography to obtain a white powder compound II (4-bromospirofluorene derivative);
[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, use toluene, methanol and water as a mixed solvent, and heat to reflux for reaction; 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 dichlorobis(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 spirofluorene derivatives. The present invention uses o-dibromobenzene as the starting material, and through lithiation reaction and ring closure reaction, 4-bromospirofluorene derivatives are efficiently synthesized. At the same time, the raw materials of this process are cheap and easily available, 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 the spiro ring 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, and 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. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.
[0026] Example 1:
[0027] This example provides a synthesis method of an aryl-silicon modified spirocyclic 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-spirobifluorene
[0031] Under argon protection, o-dibromobenzene (11.8 g), m-xylene 120 mL and methyltetrahydrofuran 40 mL were added to the 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, fluorenone (18.0 g) was added in batches, the temperature was raised to room temperature, and the reaction was carried out overnight. After the reaction was completed, 50 mL of dilute hydrochloric acid was slowly added dropwise to quench the reaction, and the mixture was 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, 30 mL of glacial acetic acid 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. After the reaction was completed, the mixture was cooled to room temperature, and a white powder was obtained by suction filtration. The white powder (7.8 g) was obtained by column chromatography purification, with a yield of 78.9% and a content of 99.8%.
[0032] (2) Synthesis of Compound 1
[0033] Under argon protection, 4-bromo-9,9-spirobifluorene (4.0 g), Compound III (3.1 g), dichlorobis(tert-butyl)-(4-dimethylaminophenyl)phosphine palladium(II) (9.3 mg), K 2 CO 3 (1.8 g), toluene (60 mL), methanol (7.5 mL) and water (30 mL) were heated to reflux and reacted for 12 h. After the reaction was completed, the mixture was extracted with dichloromethane (100 mL × 3), the organic phases were combined, the solvent was concentrated under reduced pressure, and a white solid powder (5.8 g) was obtained by column chromatography purification, with a yield of 87.8% and a content of 99.6%.
[0034] Characterization data of Compound 1: 1 H NMR (400 MHz, CDCl 3 ) δ 7.85 (d, J = 7.2 Hz, 3H), 7.75–7.53 (m, 9H), 7.47–7.41 (m, 3H), 7.41–7.28 (m, 8H), 7.17 (dd, J = 7.6, 1.2 Hz, 1H), 7.14–6.95 (m, 6H), 6.82–6.65 (m, 4H).
[0035] 13 C NMR (101 MHz, CDCl 3 ) δ 149.07, 141.65, 140.54, 137.95, 137.27, 136.60, 135.85, 134.76, 134.16, 130.54, 129.79, 128.32, 128.07, 127.98, 127.82, 127.60, 127.35, 127.27, 124.25, 123.94, 123.13, 123.06, 120.10.
[0036] Example 2:
[0037] This example provides a synthesis method of an aryl-silicon modified spiro organic optoelectronic functional material, and the reaction formula is as follows:
[0038]
[0039] The synthesis method includes the following steps:
[0040] (1) Synthesis of 4'-bromo-2,7-di-tert-butyl-9,9'-spirobi[fluorene] d
[0041] Under argon protection, add o-dibromobenzene (11.8 g), m-xylene 120 mL and methyltetrahydrofuran 60 mL to the reaction kettle, cool down to -78 °C, slowly drop in n-butyllithium (25 mL, 1.6 mol / L), stir at low temperature for 30 min, and then add 2,7-di-tert-butyl-9H-fluorenone (21.9 g) in batches, raise the temperature to room temperature, and react overnight; after the reaction is completed, slowly drop in 50 mL of dilute hydrochloric acid to quench the reaction, extract, combine the organic phases, concentrate the solvent under reduced pressure, and purify by column chromatography to obtain an alcohol intermediate. Add the alcohol intermediate to the reaction kettle, then add 30 mL of glacial acetic acid, heat to reflux, add a few drops of concentrated hydrochloric acid, react for 8 h, after the reaction is completed, cool to room temperature, filter by suction, and purify by column chromatography to obtain 9.2 g of off-white powder, with a yield of 72.1% and a content of 99.9%.
[0042] (2) Synthesis of Compound 2
[0043] Under argon protection, add 4'-bromo-2,7-di-tert-butyl-9,9'-spirobi[fluorene] (5.1 g), Compound III (2.5 g), dichlorobis(tert-butyl)-(4-dimethylaminophenyl)phosphine palladium(II) (18.4 mg), K 2 CO 3 (1.3 g), toluene (60 mL), methanol (130 mL) and water (30 mL), heat to reflux, and react for 12 h. After the reaction is completed, extract with dichloromethane (100 mL × 3), combine the organic phases, concentrate the solvent under reduced pressure, and purify by column chromatography to obtain 6.7 g of white solid powder, with a yield of 88.5% and a content of 99.5%.
[0044] Characterization data of Compound 2: 1 H NMR(500MHz,CDCl 3)δ 7.91 (t, J = 1.6 Hz, 1H), 7.75–7.69 (m, 4H), 7.68–7.62 (m, 6H), 7.59 (t, J = 7.6 Hz, 1H), 7.46–7.41 (m, 3H), 7.39–7.35 (m, 7H), 7.17 (dd, J = 7.6, 1.2 Hz, 1H), 7.10–7.03 (m, 2H), 6.97 (pd, J = 7.2, 1.6 Hz, 2H), 6.72–6.59 (m, 4H), 1.23–1.09 (m, 18H). 13 C NMR (126 MHz, CDCl 3 )δ 150.81, 137.25, 136.61, 135.79, 134.20, 130.76, 129.82, 129.59, 128.29, 128.06, 127.48, 127.24, 126.96, 124.87, 124.17, 123.32, 122.89, 120.74, 119.18, 34.96, 31.62.
[0045] Example 3:
[0046] This example provides a synthesis method of an arylsilicon-modified spiro organic optoelectronic functional material, and the reaction formula is as follows:
[0047]
[0048] The synthesis method includes the following steps:
[0049] (1) Synthesis of 4-bromospiro[fluorene-9,9'-xanthene]
[0050] Under argon protection, o-dibromobenzene (11.8 g), m-xylene 120 mL, and methyltetrahydrofuran 24 mL were added to the reaction kettle, cooled to -78 °C, and n-butyllithium (37.5 mL, 1.6 mol / L) was slowly dropped in. Stir at low temperature for 30 min, then xanthone (26.5 g) was added in batches, and the temperature was raised to room temperature, and the reaction was carried out overnight; after the reaction was completed, 50 mL of dilute hydrochloric acid was slowly 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, and the reaction was carried out for 8 h. After the reaction was completed, it was cooled to room temperature, filtered by suction, and purified by column chromatography to obtain 7.9 g of off-white powder, with a yield of 77.3% and a content of 99.5%.
[0051] (2) Synthesis of Compound 3
[0052] Under argon protection, 4-bromospiro[fluorene-9,9'-xanthene] (4.1 g), Compound III (5.2 g), dichlorobis(tert-butyl)-(4-dimethylaminophenyl)phosphine palladium(II) (32.0 mg), K 2 CO 3 (3.1 g), toluene (60 mL), methanol (1.2 mL) and water (36 mL) were heated to reflux and reacted for 12 h. After the reaction was completed, the mixture was extracted with dichloromethane (100 mL × 3), and the organic phases were combined. The solvent was concentrated under reduced pressure, and the product was purified by column chromatography to obtain 6.2 g of white solid powder with a yield of 92.4% and a purity of 99.5%.
[0053] Characterization data of Compound 3: 1 H NMR (500 MHz, CDCl 3 ) δ 7.89–7.85 (m, 1H), 7.79–7.57 (m, 9H), 7.55–7.35 (m, 9H), 7.34–7.11 (m, 9H), 7.10–6.98 (m, 2H), 6.82 (p, J = 7.2 Hz, 2H), 6.47 (dd, J = 40.0, 8.0 Hz, 2H). 13 C NMR (126 MHz, CDCl 3 ) δ 140.41, 139.84, 137.36, 136.60, 135.87, 134.81, 134.17, 130.45, 129.80, 129.77, 128.35, 128.24, 128.20, 128.17, 128.07, 127.93, 127.39, 125.84, 124.83, 123.43, 123.10, 116.87.
[0054] Example 4:
[0055] This example provides a method for synthesizing an arylsilicon-modified spiro organic optoelectronic functional material, and the reaction formula is as follows:
[0056]
[0057] The synthesis method includes the following steps:
[0058] (1) Synthesis of 4'-bromo-10,10-dimethylspiro[anthracene-9(10H),9'-[9H]fluorene]
[0059] 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, and n-butyllithium (30 mL, 1.6 mol / L) was slowly added dropwise. It was stirred at low temperature for 30 min, and then 10,10-dimethylanthrone (21.5 g) was added in batches. The temperature was raised to room temperature and the reaction was carried out overnight. After the reaction was completed, 50 mL of dilute hydrochloric acid was slowly added dropwise to quench the reaction. It was extracted, and 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, and then 30 mL of glacial acetic acid was added. It was heated to reflux, a few drops of concentrated hydrochloric acid were added, and the reaction was carried out for 8 h. After the reaction was completed, it was cooled to room temperature, filtered by suction, and 8.4 g of off-white powder was obtained by column chromatography purification. The yield was 76.2%, and the content was 99.6%.
[0060] (2) Synthesis of Compound 4
[0061] Under argon protection, 4'-bromo-10,10-dimethylspiro[anthracene-9(10H),9'-[9H]fluorene] (4.4 g), Compound III (4.1 g), dichlorobis(tert-butyl)-(4-dimethylaminophenyl)phosphine palladium(II) (6.8 mg), K 2 CO 3 (2.4 g), toluene (60 mL), methanol (12 mL) and water (40 mL) were heated to reflux and the reaction was carried out for 12 h. After the reaction was completed, it was extracted with dichloromethane (100 mL×3), the organic phases were combined, the solvent was concentrated under reduced pressure, and 6.1 g of white solid powder was obtained by column chromatography purification. The yield was 88.3%, and the content was 99.4%.
[0062] Characterization data of Compound 4: 1 H NMR(500MHz,CDCl 3 )δ7.72(d,J=3.8Hz,1H),7.58(ddd,J=11.6,7.6,2.4Hz,2H),7.54–7.48(m,6H),7.44(td,J=9.8,9.2,6.8Hz,3H),7.28(td,J=7.2,2.0Hz,3H),7.22(td,J=7.6,2.3Hz,6H),7.08–7.00(m,3H),6.96(td,J=7.6,2.4Hz,1H),6.92–6.87(m,2H),6.81–6.66(m,5H),6.18(dd,J=45.6,8.0Hz,2H),1.79(dd,J=5.6,2.8Hz,6H).
[0063] 13 C NMR(126MHz,CDCl 3)δ143.08,140.55,137.55,136.62,135.79,134.72,134.20,130.43,129.80,129.20,128.91,128.36,128.16,128.07,127.88,127.05,126.75,126.40,125.65,124.78,123.12,57.93,37.55,36.08,36.02.
[0064] Application Example 1 Preparation of Organic Electroluminescent Devices
[0065] The OLED device was prepared using Compound 2 in the examples of the present invention as the host material.
[0066] The device structure adopted was ITO / HATCN(5nm) / TAPC(30nm) / Ir(ppy) 3 :Compound 2(10wt%)(20nm) / TPBi(40nm) / LiF(0.9nm) / Al(100nm). 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;
[0067] Comparative Example 1:
[0068] The device structure adopted was ITO / HATCN(5nm) / TAPC(30nm) / Ir(ppy) 3 :mCP(10wt%)(20nm) / TPBi(40nm) / LiF(0.9nm) / Al(100nm). 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;
[0069] The structural formula of the compound in the device is as follows:
[0070]
[0071] 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.
[0072]
[0073] It can be seen that when the arylsilicon-modified spiro derivatives of the present invention are applied to organic electroluminescent devices, the organic electroluminescent devices exhibit lower driving voltages, higher luminous efficiencies, longer service lives, and better durability and reliability.
[0074] 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 spiro ring organic photoelectric functional material, characterized in that The structural formula is as follows: Wherein, R is one of the following substituents: R may be the same or different at the same time.
2. The aryl silicon modified spiro ring 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 spirocyclic 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 purification is performed by column chromatography to obtain an alcohol intermediate; the alcohol intermediate is added to a reaction kettle, glacial acetic acid and concentrated hydrochloric acid are added to react, and the reaction is heated to reflux. 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, the solvent was concentrated under reduced pressure, and the target compound was purified by column chromatography.
4. The method for synthesizing a spirocyclic 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 spirocyclic 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 spirocyclic 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.