CN114105955A

CN114105955A - Fluorospirotriphenylamine derivative compound and preparation method and application thereof

Info

Publication number: CN114105955A
Application number: CN202111557329.4A
Authority: CN
Inventors: 郑明辉; 陈文铖; 籍少敏; 霍延平; 伍昱岚; 陈绍鸿
Original assignee: Guangdong University of Technology
Current assignee: Guangdong University of Technology
Priority date: 2021-12-18
Filing date: 2021-12-18
Publication date: 2022-03-01

Abstract

The invention discloses a fluorine spiro triphenylamine derivative compound, a preparation method and application thereof, and the structural formula is

The structure is based on that triphenyltriazine is used as electron withdrawing and triphenylamine is used as electron donating, and a series of organic light-emitting small molecules of the fluorene spiro triphenylamine derivative are prepared by introducing groups with different steric hindrance into the ortho position of triazine; the fluorene spiro triphenylamine derivative has good luminous intensity and extremely high fluorescence quantum yield; the steric effect is used for regulating and controlling the excited state configuration change and non-radiative transition of the molecule, so that the molecule realizes high efficiency; can be used as a novel luminescent molecule with good performance, low cost and high luminous intensity; the fluorine spiro triphenylamine derivative compound has obvious economic value in the aspects of preparing luminescent materials, luminescent devices or intelligent materials and the like, and has full-color display and solidHas good application prospect in the field of status illumination.

Description

Fluorospirotriphenylamine derivative compound and preparation method and application thereof

Technical Field

The invention relates to the field of organic luminescent materials, in particular to a fluorene spiro triphenylamine derivative compound and a preparation method thereof.

Background

The technology of using organic light emitting materials as Organic Light Emitting Diodes (OLEDs) has wide applications in the fields of flat panel displays, smart phones, solid state lighting, and the like, owing to the significant advantages of large area and high quality display and lighting, ultrahigh resolution, ultra-fast response speed, flexibility, and the like. The method has great application potential in the fields of flat panel display, smart phones, solid luminescence and the like, and attracts wide attention of the global academic and industrial fields.

However, the performance of the exciplex-based OLED devices still falls far behind devices using conventional D-. pi. -A-type TADF materials or phosphorescent emitters. The low electroluminescent efficiency is associated with its low photoluminescence quantum efficiency (PLQY), which is a long-standing unsolved problem in such systems and has significant limitations for their future development and application.

Disclosure of Invention

The invention aims to overcome the problems of low efficiency and the like of the prior art and provides a fluorene spiro triphenylamine derivative compound subjected to different modifications, wherein the provided fluorene spiro triphenylamine derivative compound can be used as an organic luminescent material, and realizes a qualitative breakthrough in device efficiency and roll-off by adjusting the excited state configuration change of molecules and inhibiting non-radiative transition.

Another object of the present invention is to provide a method for preparing the above-mentioned fluorene spiro triphenylamine derivative compound.

In order to solve the technical problems, the invention adopts the technical scheme that:

a fluorene spiro triphenylamine derivative compound has a molecule shown as a formula (I):

wherein R is a substituent group independently selected from the following structural formulas:

one kind of (1).

The invention connects donor and acceptor units through rigid linked fluorene and introduces large steric hindrance groups at the ortho position of the acceptor, thereby limiting the donor and acceptor units in close-packed coplanar configuration, thereby controlling the change of excited state configuration of molecules and inhibiting non-radiative transition so as to realize high efficiency. A strong electron coupling between the donor and acceptor cell is also sufficient to allow efficient direct absorption of the CT state. Rigid exciplex emitters have more efficient emission than more flexible or less coupled conventional exciplexes and conventional pi-linked TADF molecules.

Therefore, the fluorene spiro triphenylamine derivative compound provided by the invention can be used as a luminescent material or an intelligent material, and has a good application prospect in the fields of full-color display and solid-state lighting.

Preferably, said R is independently selected from the following structural formulae:

one kind of (1).

The structural formula of the fluorene spiro triphenylamine derivative compound is shown as the following benezen I:

the invention also provides a preparation method of the fluorene spiro triphenylamine derivative compound, which comprises the following steps:

s1, preparing a corresponding iodo product from a benzoic acid derivative, iodobenzene diacetic acid and iodine under the action of palladium acetate;

s2, performing hydrolysis reaction on the iodo product prepared in the step S1 and methyl iodide to obtain a corresponding esterified product;

s3, preparing a corresponding biphenyl product by a Suzuki reaction of the esterification product prepared in the step S2 and pinacol ester phenylboronic acid under the action of tetratriphenylphosphine palladium;

s4, carrying out cyclization reaction on the biphenyl product obtained in the step S3 in methanesulfonic acid to obtain the corresponding fluorenone derivative.

S5, mixing the fluorenone derivative prepared in the step S4 and 2, 4-diphenyl-6- [4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl]Under the action of palladium tetratriphenylphosphine, the intermediate a is prepared by Suzuki reaction of-1, 3, 5-triazine

S6, reacting the intermediate a prepared in the step S5 with 2-bromotriphenylamine at low temperature through n-butyl lithium to prepare the fluorene spirotriphenylamine derivative

The benzoic acid derivative is

Preferably, the molar ratio of the benzoic acid derivative, the iodobenzene diacetic acid and the iodine in the step S1 is 1 (1-1.3) to 1-1.3.

Preferably, the iodination reaction temperature in the step S1 is 90-110 ℃, and the reaction time is 16-24 h.

Preferably, in step S1, the organic solvent for reaction is one of toluene, dimethyl sulfoxide and N, N-dimethylformamide.

Preferably, the molar ratio of the iodo product prepared in the step S2 in the S1 to methyl iodide is 1 (1.5-2).

Preferably, in the step S2, the hydrolysis reaction temperature is 60-90 ℃, and the reaction time is 3-6 h.

Preferably, the step S3Suzuki reaction shows that the molar ratio of the esterification product prepared by the step S2 to the pinacol ester of phenylboronic acid is 1: 1.1.

preferably, the Suzuki reaction temperature in the step S3 is 40-60 ℃, and the reaction time is 6-8 h.

Preferably, the inorganic base in the step S3Suzuki reaction is potassium carbonate.

Preferably, in step S3, the organic solvent for reaction is one of toluene, tetrahydrofuran and N, N-dimethylformamide.

Preferably, the temperature of the ring-closure reaction in the step S4 is 60-90 ℃, and the reaction time is 6-10 h.

Preferably, the molar ratio of the fluorenone derivative prepared in the step S5 or S4 to 2, 4-diphenyl-6- [4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine is 1: (1.1-1.3).

Preferably, in step S5, the organic solvent for reaction is one of toluene, tetrahydrofuran and N, N-dimethylformamide.

Preferably, in the step S5, the Suzuki reaction is performed at a temperature of 100 to 130 ℃ for 16 to 24 hours in an inert gas atmosphere.

Preferably, in step S5, the reacted alkali salt is one of sodium carbonate, potassium carbonate and cesium carbonate.

Preferably, in the step S6, the molar ratio of the intermediate a, 2-bromotriphenylamine and n-butyl lithium prepared in the step S5 is: 1: 1.2: 1.32.

preferably, in the step S6, the reaction is carried out for 1h at-78 ℃ under an inert gas atmosphere.

The fluorene spiro triphenylamine derivative compound is applied to luminescent materials, luminescent devices or intelligent materials and the like.

Compared with the prior art, the invention has the beneficial effects that:

the technical scheme provided by the invention connects a donor unit and an acceptor unit through rigid linked fluorene, and introduces a large steric hindrance group at the ortho position of the acceptor, so that the donor unit and the acceptor unit are limited in a close-packed coplanar configuration, thereby controlling the change of the excited state configuration of the molecule to enhance the RISC rate, and in addition, the nonradiative transition can be inhibited, so as to realize high efficiency. A strong electron coupling between the donor and acceptor cell is also sufficient to allow efficient direct absorption of the CT state.

Rigid exciplex emitters have very high PLQE when incorporated into a solid matrix, over 90%, compared to more flexible or less coupled traditional exciplexes. And has a similar delta E than conventional pi-linked TADF molecules_STWhile at the same time having a faster RISC rate. Therefore, the invention has good application prospect in the fields of full-color display and solid-state lighting as a luminescent material or an intelligent material.

Drawings

FIG. 1 is a NMR spectrum of compound M1 prepared in example 1 of the present invention;

FIG. 2 is a mass spectrum of compound M1 prepared in example 1 of the present invention;

FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of compound M2 prepared in example 2 of the present invention

FIG. 4 is a mass spectrum of compound M2 prepared in example 2 of the present invention;

FIG. 5 shows that the compound M1 prepared in example 1 of the present invention is at 1.0X 10^-5Ultraviolet absorption spectrum in dichloromethane solution of M;

FIG. 6 shows that the compound M1 prepared in example 1 of the present invention is at 1.0X 10^-5Fluorescence emission spectrum in toluene solution of M;

FIG. 7 shows that the compound M2 prepared in example 2 of the present invention is at 1.0X 10^-5Ultraviolet absorption spectrum in dichloromethane solution of M;

FIG. 8 shows that the compound M2 prepared in example 2 of the present invention is at 1.0X 10^-5Fluorescence emission spectrum in toluene solution of M.

Detailed Description

The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.

Example 1

This example provides a spirotriphenylamine derivative compound with a structural formula shown as M1:

the preparation method of the compound comprises the following steps:

s1.preparation of 2-chloro-4-iodo- [1,1' -biphenyl ] -3-carboxylic acid:

in a 250mL flask, 2-bromo-3-methylbenzoic acid (4.59g, 21.3mmol), palladium acetate (0.24g, 1.06mmol), iodobenzene diacetic acid (6.68g, 21.3mmol) and iodine (5.42g, 21.3mmol) were dissolved in N, N-dimethylformamide (50 mL). After stirring at 100 ℃ for 24h, the reaction mixture was cooled to room temperature and diluted with 50ml of ethyl acetate, 200ml of aqueous hydrochloric acid (0.5N) was added to wash off the N, N-dimethylformamide, and the crude product was extracted 3 times with ethyl acetate. The organic phase was collected, washed with saturated brine, and dried over anhydrous sodium sulfate. Vacuum concentrating for 30min at 0-700 mbar by a rotary evaporator, removing organic solvent, and purifying the residue by silica gel column chromatography to obtain white solid iodinated product 2-chloro-4-iodo- [1,1' -biphenyl ] -3-carboxylic acid 6.71 g. (yield: 85%)

S2.2-chloro-4-iodo- [1,1' -biphenyl ] -3-carboxylic acid methyl ester preparation;

2-chloro-4-iodo- [1,1' -biphenyl ] -3-carboxylic acid (6.71g, 18.8mmol) was dissolved in acetone (50.0mL), and potassium carbonate (5.2g, 37.6mmol) and iodomethane (4g, 28.2mmol) were added in this order. The reaction mixture was reacted under reflux for 3h and then quenched with water. Extracting the crude product with ethyl acetate for 3 times, collecting an organic phase, washing the organic phase with brine, drying the organic phase with anhydrous sodium sulfate, performing vacuum concentration for 30min at 0-700 mbar by using a rotary evaporator, and removing an organic solvent to obtain 6.64g of a product, namely 2-chloro-4-iodo- [1,1' -biphenyl ] -3-carboxylic acid methyl ester. This material was used in the next reaction without further purification. (yield: 95%)

S3.3 ' -chloro- [1,1':4', 1' -terphenyl ] -2' -carboxylic acid methyl ester preparation;

in a two-necked flask with a reflux condenser, methyl 2-chloro-4-iodo- [1,1' -biphenyl ] -3-carboxylate (6.64g, 17.9mmol), phenylboronic acid (2.2g, 17.9mmol), palladium tetrakistriphenylphosphine (1.04g, 0.9mmol) and potassium carbonate (4.5g, 35.8mmol) were added, and N, N-dimethylformamide (50mL) and water (8mL) were further added to mix, and the system was evacuated and charged with nitrogen. The resulting mixture was stirred at 55 ℃ for 7 hours, cooled to room temperature, poured into saturated brine, and extracted with ethyl acetate 3 times. The organic layer was collected, and the collected organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. Concentrating in vacuum for 30min under 0-700 mbar by a rotary evaporator, removing the organic solvent, and purifying the residue by silica gel column chromatography to obtain 4.3g of oily product 3' -chloro- [1,1':4', 1' -terphenyl ] -2' -methyl carboxylate. (yield: 75%)

S4, preparing 1-chloro-2-phenyl-9H-fluorenone;

methyl 3 '-chloro- [1,1':4',1 "-terphenyl ] -2' -carboxylate (4.3g, 13.4mmol) was dissolved in methanesulfonic acid (10 ml). The reaction was stirred at 65 ℃ for 6 hours, then quenched with water and extracted 3 times with ethyl acetate. The organic layer was collected, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated in vacuo for 30min at 0 to 700mbar by a rotary evaporator to remove the organic solvent, to give 3.6g of 1-chloro-2-phenyl-9H-fluorenone as a yellow solid (yield: 92%).

S5.preparation of 1- (4- (4, 6-biphenyl-1, 3, 5-triazine-2-phenyl) -2-phenyl-9H-fluorenone:

in a two-necked flask, 1-chloro-2-phenyl-9H-fluorenone (3.6g, 12.4mmol), 2, 4-diphenyl-6- [4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine (6g, 13.7mmol), tetrakistriphenylphosphine palladium (0.7g, 0.62mmol), and cesium carbonate (8.1g, 24.8mmol) were added under a nitrogen atmosphere. N, N-dimethylformamide (40mL) and water (8mL) were added and the system was evacuated and purged with nitrogen. Then heated and refluxed in an oil bath at 110 ℃ for 24 hours, after the reaction is finished, cooled to room temperature, and filtered to obtain 6.3g of 1- (4- (4, 6-biphenyl-1, 3, 5-triazine-2-phenyl) -2-phenyl-9H-fluorenone as a yellow solid, which is directly used in the next step. (yield: 90%)

S6.1 ' - (4- (4, 6-biphenyl-1, 3, 5-triazine-2-phenyl) -2', 10-biphenyl-10H-fluorenes Spirotriphenylamine [ acridine-9, 9' -fluorene ] preparation:

in a two-necked flask, 2-bromotriphenylamine (4.4g, 13.5mmol) was dissolved in 50mL of dehydrated tetrahydrofuran under a nitrogen atmosphere. The mixture was cooled to-78 ℃ and held for 10 minutes. 2.4M n-butyllithium (6.2ml, 14.8mmol) was then added dropwise over 10 minutes and the mixture was stirred for a further 1h at-78 ℃. Thereafter, 1- (4- (4, 6-biphenyl-1, 3, 5-triazine-2-phenyl) -2-phenyl-9H-fluorenone (6.3g, 11.2mmol) was added, and after further reaction at-78 ℃ for 15min, the mixture was slowly warmed to room temperature and stirred overnight. Then 10mL of distilled water was added to quench the reaction. The mixture was concentrated under reduced pressure to remove tetrahydrofuran, then extracted 3 times with dichloromethane, which was removed under reduced pressure. The residue was dissolved in 30mL of acetic acid, followed by the addition of 3mL of hydrochloric acid. The mixture was stirred at 110 ℃ for 4 hours. After cooling to room temperature, the mixture was poured into 100mL of ice water and filtered to give the crude product. The crude product was purified by silica gel column chromatography to give 7.5g of 1' - (4- (4, 6-biphenyl-1, 3, 5-triazine-2-phenyl) -2', 10-biphenyl-10H-fluorenes spirotriphenylamine [ acridine-9, 9' -fluorene ] as a solid product. (yield: 85%)

Example 2

This example provides a spirofluorene triphenylamine derivative compound, which is prepared in the same manner as in example 1, except that in example 1, the benzoic acid derivative used in S1 is

The structural formula of the obtained fluorene spiro triphenylamine derivative compound M2 and M2 is shown in the specification.

Performance testing

Characterization and performance test were performed on the fluorene spiro triphenylamine derivative compounds M1 and M2 obtained in examples 1 and 2.

The test method is as follows:

and (3) detecting the structure of the compound: using a Bruker 400MHz superconducting nuclear magnetic resonance instrument, wherein a solvent used by MI is deuterated chloroform, and a solvent used by M2 is deuterated dimethyl sulfoxide;

mass spectrum detection: m1 obtained in example 1 and M2 obtained in example 2 were dissolved in dichloromethane to prepare a solution with a concentration of 1mg/mL, and mass spectrometry was performed using a Saimer flying Q active ultra high resolution quadrupole combined electrostatic field orbitrap LC MS.

And (3) ultraviolet absorption spectrum detection: using Shimadzu ultraviolet visible spectrophotometer UV-2700, the scanning range was

200～700nm；

And (3) emission spectrum detection: using a steady state/transient state fluorescence spectrometer (FLS980), the excitation wavelength was 285nm,

under the protection of nitrogen, the testing temperature is 300K.

The test results were as follows:

the molecular hydrogen spectrum of the fluorene spiro triphenylamine derivative compound M1 prepared in example 1 is shown in fig. 1. It can be seen that: 1H NMR (400MHz, CDCl3) δ 8.78,8.77,8.76,8.23,8.18,8.16,7.98,7.96,7.88,7.87,7.78,7.65,7.64,7.63,7.62,7.61,7.61,7.60,7.59,7.58,7.57,7.56,7.56,7.52,7.37,7.37,7.36,7.35,7.34,7.33,7.26,7.23,7.21,7.20,7.19,7.18,7.15,7.15, molecular hydrogen spectrum peaks can correspond to the target product one-to-one, and are reasonable in number; from the mass spectrum (FIG. 2), it can be seen that the relative molecular mass in the graph is 791.31705, plus one H, consistent with the relative molecular mass of the synthesized M1. The results of the nuclear magnetic resonance and mass spectrometry combined indicate that the product obtained in example 1 was M1.

The molecular hydrogen spectrum of the fluorene spiro triphenylamine derivative compound M2 prepared in example 2 is shown in fig. 3. It can be seen that: 1H NMR (400MHz, DMSO) δ 8.78,8.77,8.31,8.29,8.02,8.00,7.98,7.76,7.74,7.71,7.70,7.68,7.50,7.48,7.38,7.36,7.34,7.25,7.24,7.19,7.18,7.13,7.12,7.05,7.03,6.87,6.85,6.83,6.57,6.55,6.53,6.43,6.41,6.24,6.22,5.75,5.73,5.32,1.97, molecular hydrogen spectrum peaks can correspond to the target product one to one, in reasonable amounts; from the mass spectrum (FIG. 4), it can be seen that the relative molecular mass in the graph is 729.30039, plus one H, consistent with the relative molecular mass of the synthesized M2. The results of the nuclear magnetic and mass spectra were combined to show that the product obtained in example 2 was M2.

M1 and M2 obtained in example were dissolved in Tetrahydrofuran (THF) solution using Shimadzu ultraviolet-visible spectrophotometer UV-2700 to prepare 1X 10^-3Diluting the mother liquor to 1 × 10^-5The mol/L is tested.

FIG. 5 shows M1 at 1X 10 prepared in example 1^-5Ultraviolet-visible absorption spectrum in mol/L dichloromethane. As can be seen from FIG. 5, the main absorption peak position of M1 was 278 nm.

FIG. 6 shows M2 at 1X 10 prepared in example 2^-5Ultraviolet-visible absorption spectrum in mol/L dichloromethane. As can be seen from FIG. 6, the main absorption peak position of M2 was 278 nm.

Fluorescence emission spectroscopy was used: FLS980 fluorometer, M1 and M2 prepared in example were dissolved in Tetrahydrofuran (THF) to prepare 1X 10^-3mol/L of the mother liquor, when tested, diluted to 1X 10^-5mol/L。

FIG. 7 shows M1 at 1X 10 prepared in example 1^-5Fluorescence emission spectrum in mol/L toluene. As can be seen from FIG. 7, the main emission peak position of M1 was 475 nm.

FIG. 8 shows M2 at 1X 10 prepared in example 2^-5Fluorescence emission spectrum in mol/L toluene. From fig. 8, the main emission peak position of M1 is 497 nm.

In conclusion, the fluorene spiro triphenylamine derivative compound provided by the invention realizes blue light emission (M1 is blue light emission, and M2 is sky blue light emission), and can be used as a novel OLED light-emitting molecule with good performance and low cost. The fluorene spiro triphenylamine derivative compound has obvious economic value in the application aspects of preparing luminescent materials, luminescent devices or intelligent materials and the like, and has good application prospect in the fields of full-color display and solid-state lighting.

Meanwhile, the invention realizes the controllable preparation of the fluorene spiro triphenylamine derivative compound; the preparation cost is low, the raw material source is wide, large-scale production can be realized, and the method has wide commercialization prospect.

Claims

1. A fluorine spiro triphenylamine derivative is characterized by having a molecular structure shown as a formula (I):

one kind of (1).

2. The fluorene spiro triphenylamine derivative of claim 1, wherein R is independently selected from the following structural formulas:

one kind of (1).

3. A method for producing a fluorene spiro triphenylamine derivative according to claim 1, comprising the steps of:

s1, preparing a corresponding iodo product from a benzoic acid derivative, iodobenzene diacetic acid and iodine under the catalytic action of palladium acetate;

s3, preparing the esterification product obtained in the step S2 and a corresponding esterification product of biphenyl and a pinacol ester of phenylboronic acid through a Suzuki reaction under the action of palladium tetratriphenylphosphine;

S5, reacting the fluorenone derivative prepared in the step S4 and 2, 4-diphenyl-6- [4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine under the action of palladium tetratriphenylphosphine to prepare an intermediate a through a Suzuki reaction;

s6, reacting the intermediate a prepared in the step S5 with 2-bromotriphenylamine at-78 ℃ through n-butyl lithium to prepare the fluorene spirotriphenylamine derivative

The benzoic acid derivative is

4. The method for producing a fluorenylspirotriphenylamine derivative according to claim 2, wherein the molar ratio of the benzoic acid derivative to the iodophenylenediacetic acid to iodine in step S1 is 1: (1-1.2): (1-1.2), the reaction temperature is 90-110 ℃, and the reaction time is 15-24 h.

5. The method for preparing the fluorene spiro triphenylamine derivative according to claim 2, wherein in the step S2, the reaction temperature is 50-70 ℃ and the reaction time is 3-6 hours.

6. The method for preparing the fluorene spiro triphenylamine derivative according to claim 2, wherein in the step S3, the reaction temperature is 40-60 ℃ and the reaction time is 6-8 h.

7. The method for preparing the fluorene spiro triphenylamine derivative according to claim 2, wherein in the step S4, the reaction temperature is 60 to 100 ℃ and the reaction time is 6 to 9 hours.

8. The method for producing a fluorenylspirotriphenylamine derivative according to claim 2, wherein the molar ratio of the fluorenone derivative to 2, 4-diphenyl-6- [4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine in step S5 is 1: (1.1-1.3), the reaction temperature is 90-110 ℃, and the reaction time is 20-24 h.

9. The method for preparing a fluorene spirotriphenylamine derivative according to claim 2, wherein the molar ratio of the intermediate a to 2-bromotriphenylamine to n-butyllithium in step S6 is 1 (1-1.3): (1.3-1.4), the reaction is carried out at-78 ℃ for 1h in an inert gas atmosphere, and the reaction is transferred to room temperature overnight.

10. Use of the fluorene spiro triphenylamine derivative according to claim 1 in a luminescent material, a luminescent device or an intelligent material.