CN113896675A - Organic luminescent material based on carbazole-triphenylamine derivative and preparation method thereof - Google Patents

Abstract

The present case relates to an organic photoelectric material based on carbazole-triphenylamine derivatives and a preparation method thereof, the material is prepared by taking carbazole derivatives, triphenylamine derivatives, boron ester compounds and triethyl phenylphosphonite as construction units through intermolecular nucleophilic substitution reaction, palladium catalytic coupling reaction and twisting-horner reaction, and is purified through column chromatography or recrystallization, and the material molecules have the following structural general formula:

Description

Organic light-emitting materials based on carbazole-triphenylamine derivatives and preparation methods thereof

technical field

The invention relates to the fields of organic photoelectric functional materials and organic synthesis, in particular to an organic photoelectric material based on a carbazole-triphenylamine derivative and a preparation method thereof.

Background technique

Organic photoluminescent materials are mainly some organic conjugated small molecules or macromolecules. Organic conjugated small molecules have the characteristics of wide tunable emission wavelength range, easy modification, and simple preparation. By introducing electron-donating groups such as nitrogen-containing groups, aromatic rings, and strong electron-withdrawing structures such as cyano groups, carboxylic acids, and halogens into the molecule, the degree of conjugation and intramolecular charge distribution of the system can be changed, thereby constructing a push-pull electron structure. Molecules, further push-pull electron pairs and the change of the energy band of the π-conjugated system will then change the optoelectronic properties of the compound. Organic light-emitting molecules with triphenylamine as the donor group have good film formation and solubility, and have good charge transport ability and high oxidation potential, so they are candidates for organic optoelectronic functional materials; recently carbazole and its derivatives Because of its unique luminescent properties, it has become a star molecule for the construction of long-lived phosphorescent materials.

In recent years, the research of organic light-emitting materials has mainly focused on the research of organic fluorescent materials, and organic fluorescent materials usually have the problem of short light-emitting life. Therefore, the construction of long-life light-emitting materials is the main goal of the present invention. The present invention selects triphenylamine, carboxylate A series of luminescent materials with novel structure and excellent optoelectronic properties were prepared by simple chemical modification.

SUMMARY OF THE INVENTION

In view of the deficiencies in the prior art, the present invention aims to construct and synthesize a push-pull long-life luminescent material based on carbazole-triphenylamine derivatives.

To achieve the above object, the present invention provides the following technical solutions:

An organic optoelectronic material based on carbazole-triphenylamine derivatives, the material uses carbazole derivatives, triphenylamine derivatives, boron ester compounds, and triethyl phenyl phosphinate derivatives as building blocks, and through intermolecular It is prepared by nucleophilic substitution reaction, palladium-catalyzed coupling reaction and witting-horner reaction, purified by column chromatography or recrystallization, and the material molecule has the following general structural formula:

in,

The present invention further provides a method for preparing the above-mentioned carbazole-triphenylamine derivative organic photoelectric material, comprising the following steps:

step one,

Under nitrogen protection, carbazole compounds were added to the reaction flask, 4,4'-bis-iodo-4"-bromotriphenylamine or 4,4'-bis-iodo-4"-aldehyde triphenylamine was added to potassium iodide/ Potassium carbonate is used as a catalyst, dimethylacetamide is used as a solvent, and the reaction is carried out in an oil bath at 160-165 ° C for 48 hours to obtain a carbazole-triphenylamine bromide compound or a carbazole-triphenylamine aldehyde compound;

Step two,

Under nitrogen protection, the carbazole-triphenylamine aldehyde compound, triethyl phenylphosphonite derivative and sodium hydride were dissolved in DMF, and the temperature was slowly raised to 85-100 ° C for 24 hours. After the reaction was completed, separation and purification were obtained to obtain the formula 1) the target compound shown;

Under nitrogen protection, add carbazole-triphenylamine bromide compound, boron ester compound, potassium carbonate and tetrakistriphenylphosphine palladium into the reaction flask, add DMSO to dissolve it, and react at 85-100 ° C for 24 hours, the reaction ends After separation and purification, the target compound represented by formula 2) is obtained.

Preferably, the step of separation and purification in the first step is as follows: after the reaction is completed, cooling to room temperature, pouring the reaction solution into water, after acidification, a large amount of solid is precipitated, suction filtration under reduced pressure, and recrystallization in ethanol.

Preferably, the step of separation and purification in the second step is: after the reaction is completed, pour it into ice water, adjust the pH to a weak acid, and then a solid is precipitated, filter under reduced pressure, dry, and perform column chromatography with dichloromethane/petroleum ether .

所述硼酯类化合物为

Preferably, the triethyl phenylphosphinate derivative is

The boron ester compound is

The preparation process of the present invention can be represented by the following general formula:

1) Synthesize the compound shown in formula 1):

2) synthesizing the compound shown in formula 2):

The beneficial effects of the present invention are as follows: the present invention selects carbazole with phosphorescence as a modification group, and prepares phosphorescent materials with higher fluorescence quantum yield and longer luminescence life through chemical modification. Compared with the prior art, the luminescence life of the material is longer long, good light stability. In addition, the material synthesis route of the present invention is short, the reaction conditions are not harsh, the equipment requirements are low, the main source of the reaction raw materials is the market, the price is relatively low, the source is wide, and the yield of the prepared material is high, and the present invention enriches and develops phosphorescent materials. research provides a reference.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present invention.

In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

Example 1:

step 1:

Under nitrogen protection, in a 100mL two-necked flask, add compound carbazolamine 8.5g (51mmol), 4,4'-bis-iodo-4"-bromotriphenylamine 13.3g (25mmol), potassium iodide (4.8g), o-Ferro Lin (10g) potassium carbonate (5g) was dissolved in 100ml of DMAC, and reacted in an oil bath at 160-165°C for 48 hours. The reaction progress was detected by thin-layer chromatography, and after the reaction was completed, it was cooled to room temperature, and the reaction solution was poured into 80ml In water, vacuum filtered and recrystallized from ethanol to obtain compound KZ-BR, 14.6g, yield: 88%. δ8.16(d, J=7.7Hz, 4H), 7.78(d, J=8.64Hz, 2H ), 7.60 (d, J=8.67Hz, 4H), 7.51-7.40 (m, 12H), 7.32-7.26 (m, 6H).

Step 2

Under nitrogen protection, compound KZ-BR (8.0 g, 12.2 mmol), 3,5-trifluoromethyl boron ester compound (4.2 g, 13 mmol), tetrakistriphenylphosphine palladium (0.012 g), potassium carbonate ( 1.7g, 13mmol), dissolved in 100ml of DMSO, bubbled with nitrogen for 15-30min, then slowly warmed up to 85-100°C and incubated for 24 hours, chromatographically detected and tracked the reaction progress, after the reaction finished, poured the reaction solution into 30ml of ice water, After adjusting pH to weak acidity with hydrochloric acid, a large amount of green solid was precipitated, which was extracted under reduced pressure, and a light yellow solid KZ-SF 8.2 g was obtained by using dichloromethane/petroleum ether as mobile phase column chromatography, yield: 82%. ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.33-8.24 (s, 3H), 8.20 (d, J=7.7 Hz, 4H), 7.88 (d, J=8.64 Hz, 2H), 7.62 (d, J= 8.67Hz, 4H), 7.54-7.43 (m, 12H), 7.34-7.28 (m, 6H).

Example 2

step 1

Replacing 4,4'-bis-iodo-4"-bromotriphenylamine in step 1 of Example 1 with 4,4'-bis-iodo-4"-aldehyde triphenylamine to obtain KZ-CHO with a yield of 86%, ¹ H NMR (300 MHz, CDCl ₃ ) δ: 9.93 (s, 1H), 8.16 (s, 4H), 7.86 (d, J=8.5 Hz, 2H), 7.62 (d, J=8.49 Hz, 4H), 7.54 -7.45(m, 12H), 7.31(d, J=8.19Hz, 2H), 1.50(s, 36H).

Step 2

Synthesis of KZ-SFL, under nitrogen protection, compound KZ-CHO (6.5g, 7.8mmol), 3,5-trifluoromethylphenylphosphinate (2.7g, 8mmol), NaH (1.2g, 20mmol), Dissolved in 100ml of DMF, bubbled with nitrogen for 30min, then slowly heated to 85-100°C for 24 hours, chromatographically detected and tracked the reaction process, after the reaction was over, poured the reaction solution into 30ml of ice water, and adjusted the pH to weakly acidic with hydrochloric acid There is a large amount of solid precipitation, which is obtained by vacuum pumping, and a light yellow solid KZ-SFL 6.9g is obtained with dichloromethane/petroleum ether as mobile phase column chromatography, yield 85%, δ: 8.18 (s, 4H), 7.88 ( d, J=8.5Hz, 2H), 7.64 (d, J=8.49Hz, 4H), 7.59-7.56 (s, 3H), 7.56-7.46 (m, 12H), 7.32 (d, J=8.19Hz, 2H) ), 6.59-6.56 (d, J=9Hz, 2H), 1.54 (s, 36H).

Example 3

step 1

Synthetic yield of KZ-BR: 88%. δ8.16(d,J＝7.7Hz,4H),7.78(d,J＝8.64Hz,2H),7.60(d,J＝8.67Hz,4H),7.51-7.40(m,12H),7.32-7.26 (m, 6H).

Step 2

Synthetic yield of KZ-COH: 80%. ¹ H NMR (300 MHz, CDCl ₃ ) δ 11.20 (s, 2H), 8.34-8.24 (s, 3H), 8.22-7.98 (d, J=7.7 Hz, 4H), 7.88-7.82 (d, J=8.64 Hz, 2H), 7.66 (d, J=8.67 Hz, 4H), 7.56-7.44 (m, 12H), 7.35-7.30 (m, 6H).

Example 4

step 1

Synthesis of KZ-CHO, 86% yield, ¹ H NMR (300 MHz, CDCl ₃ ) δ: 9.93 (s, 1H), 8.16 (s, 4H), 7.86 (d, J=8.5 Hz, 2H), 7.62 ( d, J=8.49Hz, 4H), 7.54-7.45 (m, 12H), 7.31 (d, J=8.19Hz, 2H), 1.50 (s, 36H).

Step 2

Synthesis of SKZ-B, 86% yield, δ: 8.18(s, 4H), 7.88(d, J=8.5Hz, 2H), 7.74-7.68(d, J=9.0Hz, 4H), 7.64(d, J=8.49Hz, 4H), 7.56-7.46 (m, 12H), 7.34 (d, J=8.2Hz, 2H), 6.59-6.56 (d, J=9Hz, 2H), 1.56 (s, 36H).

Material fluorescence and UV spectrum test: configure the molecule into a THF solution with a concentration of 10 ^-5 to 10 ^-6 mol/L, use a UV absorption spectrometer and a fluorescence spectrometer to measure the absorption spectrum and emission spectrum of the material, and calculate its fluorescence quantum yield , the following table 1 is the spectral data of the corresponding molecule.

Table 1

compound Maximum absorption λ_{wavelength nm} Maximum emission λ_{wavelength nm} Fluorescence quantum yield Phosphorescence lifetime (s) KZ-SF 456 520 0.78 1.2 KZ-SFL 456 510 0.84 2.0 KZ-COH 450 524 0.78 2.1 SKZ-B 450 532 0.84 2.2

Combined with Examples 1-4, the reaction conditions designed by the present invention are mild, the reaction is efficient, the operation is simple, and the applicability is wide, which provides a new reference for enriching and developing phosphorescent materials.

Although the embodiment of the present invention has been disclosed as above, it is not limited to the application listed in the description and the embodiment, and it can be applied to various fields suitable for the present invention. For those skilled in the art, it can be easily Therefore, the invention is not limited to the specific details without departing from the general concept defined by the appended claims and the scope of equivalents.

Claims (6)

1. an organic photoelectric material based on carbazole-triphenylamine derivative, it is characterized in that, this material is with carbazole derivative, triphenylamine derivative, boron ester compound, phenylphosphonite triethyl ester derivative as The building block is prepared by intermolecular nucleophilic substitution reaction, palladium-catalyzed coupling reaction and witting-horner reaction, and purified by column chromatography or recrystallization. The material molecule has the following general structural formula:

where, R ₁ =H,

2. the preparation method of carbazole-triphenylamine derivative organic photoelectric material as claimed in claim 1, is characterized in that, comprises the steps: step one, Under nitrogen protection, carbazole compounds were added to the reaction flask, 4,4'-bis-iodo-4"-bromotriphenylamine or 4,4'-bis-iodo-4"-aldehyde triphenylamine was added to potassium iodide/ Potassium carbonate is used as a catalyst, dimethylacetamide is used as a solvent, and the reaction is carried out in an oil bath at 160-165 ° C for 48 hours to obtain a carbazole-triphenylamine bromide compound or a carbazole-triphenylamine aldehyde compound; Step two, Under nitrogen protection, the carbazole-triphenylamine aldehyde compound, triethyl phenylphosphonite derivative and sodium hydride were dissolved in DMF, and the temperature was slowly raised to 85-100 ° C for 24 hours. After the reaction was completed, separation and purification were obtained to obtain the formula 1) the target compound shown; Under nitrogen protection, add carbazole-triphenylamine bromide compound, boron ester compound, potassium carbonate and tetrakistriphenylphosphine palladium into the reaction flask, add DMSO to dissolve it, and react at 85-100 ° C for 24 hours, the reaction ends After separation and purification, the target compound represented by formula 2) is obtained. 3. the preparation method of carbazole-triphenylamine derivative organic photoelectric material as claimed in claim 2, is characterized in that, the step of separating and purifying in described step 1 is: after reaction finishes, cooling to room temperature, pouring reaction solution After pouring into water, a large amount of solid precipitated out after acidification, filtered under reduced pressure and recrystallized in ethanol. 4. the preparation method of carbazole-triphenylamine derivative organic photoelectric material as claimed in claim 2, is characterized in that, the step of separating and purifying in described step 2 is: after reaction finishes, pour into ice water, adjust pH to After weak acidity, a solid was precipitated, which was filtered off under reduced pressure, dried, and then chromatographed on a dichloromethane/petroleum ether column. 5. The preparation method of carbazole-triphenylamine derivative organic photoelectric material as claimed in claim 2, wherein the triethyl phenylphosphonite derivative is

6. The preparation method of carbazole-triphenylamine derivative organic photoelectric material as claimed in claim 2, wherein the boron ester compound is