CN113683601B - Diaza-benzo-fluoranthene compound and preparation method and application thereof - Google Patents

Abstract

The invention discloses a diazobenzofluoranthene compound and a preparation method and application thereof. Pyrazine is used as an electron withdrawing body, and a plurality of different electron donors (D) are introduced to form a compound having D-A or D-π- A charge-transfer light-emitting material that gives the acceptor structure, realizes wide spectral range (531-713nm) with adjustable light emission color, and the fluorescence quantum yield can reach up to 96%. It is a new type of light-emitting molecule with good performance and low cost. The preparation of light-emitting materials, light-emitting devices or smart materials has significant economic value, and has good application prospects in the fields of full-color display and solid-state lighting.

Description

A kind of diazobenzofluoranthene compound and its preparation method and application

technical field

The present invention relates to the technical field of organic light-emitting materials, and more particularly, to a diazobenzofluoranthene compound and a preparation method and application thereof.

Background technique

The technology of organic light-emitting materials used as organic light-emitting diodes (OLEDs) has a wide range of applications in flat-panel displays, smartphones, and solid-state light emitting. Significant advantages such as ultra-fast response speed and flexibility. It has huge application potential in the fields of flat panel display, smart phone and solid-state light-emitting, attracting extensive attention from academia and industry around the world.

At present, most organic light-emitting materials are blue and green light-emitting materials, and there are few studies on orange/red materials. For example, CN112961148A discloses an organic thermally induced delayed fluorescent material based on pyrazine acceptor and its preparation method and application. Taking the acceptor as the core, four organic thermally induced delayed fluorescent materials were synthesized, which have good thermal stability and tunable emission color, and can be used in orange/red TADF OLED emitters, but their spectral range (580-620nm) is narrow.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the defects and deficiencies of the existing organic light-emitting materials with a narrow emission color spectrum, and provide a diazobenzofluoranthene compound, which introduces a plurality of electron donors into the diazobenzofluoranthene system, and adjusts the The type and position of the electron donor can realize the tunable emission color in a wide spectral range, and at the same time obtain a high fluorescence quantum yield.

Another object of the present invention is to provide a method for preparing a diazobenzofluoranthene compound.

Another object of the present invention is to provide an application of a diazobenzofluoranthene compound in the preparation of luminescent materials and smart materials.

The above-mentioned purpose of the present invention is achieved through the following technical solutions:

A diazobenzofluoranthene compound, the molecular structure of which is shown in the general formula (I):

Wherein, R is H or CN, D ₁ and D ₂ are electron donor groups, and D ₁ and D ₂ are respectively selected from any one of the following structural formulas:

Preferably, the diazobenzofluoranthene compound is selected from any one of the following structural formulas:

Preferably, the structural formula of the diazobenzofluoranthene compound is:

时，则构成具有D-π-A结构的电荷转移有机发光材料，引入

等其他基团时，则构成具有D-A结构的电荷转移有机发光材料。The present invention is based on the diazobenzofluoranthene system, takes the pyrazine part as the electron acceptor (A), and introduces multiple groups D ₁ and D ₂ with electron donating ability into it to form a DA or D-π-A structure The charge-transfer organic light-emitting materials, for example, introduce

, then a charge-transfer organic light-emitting material with a D-π-A structure is formed, and the introduction of

and other groups, it constitutes a charge-transfer organic light-emitting material with a DA structure.

Multiple different electron donors and electron acceptors build multiple charge transfer channels to enhance intramolecular charge transfer, and the torsion angles generated by multiple electron donors and the central benzene nucleus are beneficial to reduce the frontier molecular orbitals. overlapping, thereby reducing the single-triplet energy range, effectively promoting the reverse intersystem crossing process, and improving the performance of thermally activated delayed fluorescence. The strong interaction between D-A or D-π-A structures is conducive to the realization of long-wave emission and a variety of light color tunability, from green to red light color tunable (wavelength from 531 to 713nm), while obtaining high fluorescence quantum yield.

等)，由于弱给电子体和中心苯核形成的扭转角相较于强给电子体和中心苯核形成的扭转角更小，使得分子堆积相比平面分子没有那么紧密，有利于抑制π-π堆积发生分子猝灭导致不发光的情况发生，从而更有利于实现长波发射以及多种光色可调的效果，克服现有技术具有D-A结构或D-π-A结构的长波发射小分子一般只能采用强给电子基团、且发光颜色单一的技术难题，实现发光颜色可调的长波发射。At the same time, D ₁ and D ₂ can choose groups with poor electron donating ability as electron donors (such as

etc.), since the torsion angle formed by the weak electron donor and the central benzene nucleus is smaller than that formed by the strong electron donor and the central benzene nucleus, the molecular packing is less dense than that of the planar molecule, which is beneficial to suppress the π- Molecular quenching caused by π stacking leads to the occurrence of no light emission, which is more conducive to the realization of long-wave emission and a variety of light color tunable effects, overcoming the general long-wave emission of small molecules with DA structure or D-π-A structure in the prior art. Only the technical difficulties of strong electron-donating groups and single emission color can be used to realize long-wave emission with adjustable emission color.

In addition, in the central benzene nucleus of the present invention, it is beneficial to make the two R groups present a plane rigid structure, reduce the rotation and vibration of molecular bonds, inhibit molecular relaxation, and reduce non-radiative transitions, so that the diazobenzofluoranthene Such compounds achieve more stable and higher fluorescence quantum yields.

A preparation method of a diazobenzofluoranthene compound, comprising the following steps:

S1. adopt 1,4-dibromo-2,3-difluorobenzene and fuming nitric acid to carry out nitration reaction in trifluoromethanesulfonic acid to obtain 1,4-dibromobenzene-2,3-difluoro-5, 6-dinitrobenzene;

S2. 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene in S1 is placed in acetic acid and iron powder is added to carry out reduction reaction to obtain 3,6-dibromobenzene- 4,5-difluoro-1,2-phenylenediamine;

S3. 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine and acenaphthylene quinone compounds in S2 are placed in acetic acid for condensation reaction to obtain intermediate α:

S4. Co-dissolve the intermediate α, the basic salt, the palladium-containing coupling agent and the electron donor group D ₁ in the organic solvent in S3, and carry out a heating reaction to obtain the intermediate β:

S5. Co-dissolve the intermediate β, the basic salt and the electron donor group D ₂ in S4 in an organic solvent, and carry out a heating reaction to obtain a diazobenzofluoranthene compound:

缩合反应温度为100～125℃，反应时间为8～16h；S4中加热反应需在惰性气氛中进行，加热温度为120～180℃，加热反应时间为12～24h；S5中加热反应需在惰性气氛中进行，加热温度为100～150℃，加热反应时间为12～24h。Among them, the nitration reaction temperature in S1 is 50-70 °C, and the reaction time is 24-36 h; the reduction reaction temperature in S2 is 40-60 °C, and the reaction time is 6-8 h; the acenaphthylene quinone compounds in S3 are

The condensation reaction temperature is 100～125℃, and the reaction time is 8～16h; the heating reaction in S4 needs to be carried out in an inert atmosphere, the heating temperature is 120～180℃, and the heating reaction time is 12～24h; in S5, the heating reaction needs to be carried out in an inert atmosphere Carry out in the atmosphere, the heating temperature is 100～150 ℃, and the heating reaction time is 12～24h.

Preferably, the molar ratio of 1,4-dibromo-2,3-difluorobenzene, fuming nitric acid and trifluoromethanesulfonic acid in S1 is 1:(6~9):(40~70), more preferably the molar ratio The ratio is 1:8:50.

Preferably, the molar ratio of 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene, reduced iron powder and acetic acid in S2 is 1:(10～20):(100～175 ), more preferably the molar ratio is 1:15:150.

Preferably, the molar ratio of 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine to the acenaphthylenequinone compound in S3 is 1:(0.8-1.2), more preferably the molar ratio is 1 :1.

Preferably, the molar ratio of intermediate α, basic salt, palladium-containing coupling agent and electron donor group in S4 is 1:(25-50):(0.1-0.15):(2-2.5), more preferably The molar ratio was 1:40:0.12:2.3.

Preferably, the molar ratio of the intermediate β, the basic salt and the electron donor group in S5 is 1:(20-50):(2-4), and more preferably the molar ratio is 1:40:3.

Preferably, the basic salt in S4 is one or more of sodium carbonate, potassium carbonate and potassium tert-butoxide.

Preferably, the palladium-containing coupling agent in S4 is tetrakis(triphenylphosphorus)palladium, palladium acetate, bis(dibenzylideneacetone)palladium and 1,1'-bisdiphenylphosphinoferrocene palladium dichloride one or more of them.

Preferably, the organic solvent in S4 is one or more of toluene, dimethyl sulfoxide, N,N-dimethylformamide and ethanol.

Preferably, the organic solvent in S5 is one or more of toluene, dimethyl sulfoxide and N,N-dimethylformamide.

Preferably, the basic salt in S5 is one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium tert-butoxide and sodium hydroxide.

Application of a diazobenzofluoranthene compound in light-emitting materials, light-emitting devices or smart materials.

Compared with the prior art, the present invention has the following beneficial technical effects:

The invention provides a diazobenzofluoranthene compound, which uses the pyrazine part of the diazobenzofluoranthene compound as an electron withdrawing body, and introduces a plurality of electron donors (D) to form a D-A or D-π The charge-transfer state compound of the -A structure realizes tunable emission color, wide spectral range (531-713 nm), and fluorescence quantum yield of up to 96%.

The invention provides a preparation method of diazobenzofluoranthene compounds. By adjusting the reaction temperature, the reaction time and the molar ratio of each reactant, the yield of the diazobenzofluoranthene compounds can reach up to 57%. .

The diazobenzofluoranthene compound prepared by the invention has significant economic value in applications such as preparing luminescent materials and smart materials, and has good application prospects in the fields of full-color display and solid-state lighting.

Description of drawings

Fig. 1 is the synthetic route diagram of diazobenzofluoranthene compound in embodiment 1;

Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the diazobenzofluoranthene compound in Example 1;

Fig. 3 is the mass spectrogram of diazobenzofluoranthene compound in embodiment 1;

Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of diazobenzofluoranthene compound in embodiment 7;

Fig. 5 is the mass spectrogram of diazobenzofluoranthene compound in embodiment 7;

Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of diazide benzofluoranthene compound in embodiment 8;

Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of the diazide benzofluoranthene compound in Example 9;

Fig. 8 is the ultraviolet absorption spectrum of the diazobenzofluoranthene compound in the tetrahydrofuran solution of 1.0 × 10 ^-5 mol/L in Example 1;

Fig. 9 is the ultraviolet absorption spectrum of the diazobenzofluoranthene compound in the tetrahydrofuran solution of 1.0 × 10 ^-5 mol/L in Example 7;

Figure 10 is the fluorescence emission spectrum of the diazobenzofluoranthene compound in the tetrahydrofuran solution of 1.0×10 ^-5 mol/L in Example 1;

11 is the fluorescence emission spectrum of the diazobenzofluoranthene compound in Example 7 in a 1.0×10 ⁻⁵ mol/L tetrahydrofuran solution.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.

Example 1

A diazobenzofluoranthene compound, its structural formula is as follows:

The synthetic route of this compound is shown in Figure 1, and its preparation method comprises the following steps:

Preparation of S1.1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene:

The three-necked flask (250 mL), spherical condenser, atmospheric dropping funnel, glass stopper and stirring bar were put into an oven, and dried at 100° C. for 30 min. The dried three-necked flask was taken out, 50 mL of trifluoromethanesulfonic acid was added dropwise to it, 2.5 mL of fuming nitric acid was slowly added, and the ice bath was stirred for 30 min; then, 18.4 mmol of 1,4-dibromo-2 was added within 30 min. , 5 g of 3-difluorobenzene, stirred at room temperature for 2 h, cooled the mixture to 0 °C, slowly added 2.5 mL of fuming nitric acid, heated to 70 °C and reacted for 30 h; finally, added sodium hydroxide under ice bath conditions to adjust the pH The value was adjusted to 7, filtered and collected to obtain a light yellow solid with a mass of 4.6 g (75% yield);

The molar ratio of 1,4-dibromo-2,3-difluorobenzene, fuming nitric acid and trifluoromethanesulfonic acid is 1:8:50.

Preparation of S2, 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine:

1,4-Dibromobenzene-2,3-difluoro-5,6-dinitrobenzene (3g) and iron powder (14eq) were added to a 250mL double-necked round-bottom flask, vacuumed and passed through nitrogen; then, added Acetic acid (70 mL) was added and the temperature was raised to 45°C while stirring, reacted for 6 h, cooled to room temperature, poured the reaction solution into 5% NaOH solution (180 mL), and extracted three times with ethyl acetate; finally, with saturated hydrogen carbonate The ethyl acetate layer was washed with sodium solution, then dried with anhydrous sodium sulfate, and the ethyl acetate was removed by distillation under reduced pressure to obtain a black solid. ;

The molar ratio of 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene, iron powder and acetic acid is 1:15:150.

S3. Preparation of intermediate α:

3,6-Dibromobenzene-4,5-difluoro-1,2-phenylenediamine (1g), acenaphthylenequinone (0.72g), iron powder (1.8g) and acetic acid (30mL) were added to a 100mL double neck circle In the bottom flask, stirred and heated to 125°C under nitrogen protection, and reacted for 12h. After the reaction was completed, it was cooled to room temperature, the mixture in the double-necked round-bottomed flask was placed in a Buchner funnel with filter paper, the filter residue was washed with water and ethanol, and then the filter residue was further washed with dichloromethane, and the brown solid α was collected. was 1.3 g (87% yield);

3，6-二溴苯-4，5-二氟-1，2-苯二胺和苊醌类化合物的摩尔比为1：1。The structural formula of acenaphthenequinone is

The molar ratio of 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine and acenaphthylene quinone compound is 1:1.

S4, the preparation of intermediate beta:

Intermediate α (1 g, 2.23 mmol), D1 (4-(9-carbazolyl) phenylboronic acid 1.47 g, 5.13 mmol), sodium carbonate (4.2 g) and tetrakis(triphenylphosphonium)palladium (0.3 g) Add 250mL double neck round bottom flask, then add 35mL toluene solution, 20mL ethanol and 10mL water, stir and heat to 100 ℃ and react for 12h; after the reaction, cool to room temperature, remove the solvent in the mixture by vacuum distillation; Methyl chloride and petroleum ether were used as developing solvents to carry out silica gel column chromatography separation to obtain yellow solid β with a mass of 1.4 g (yield 82%);

The molar ratio of intermediate α, basic salt, palladium-containing coupling agent and electron donor group D ₁ is 1:40:0.12:2.3.

S5. Preparation of diazobenzofluoranthene compounds:

Intermediate beta (0.5g), D2 ₍ carbazole 0.25g) and potassium carbonate (0.3g) were added to a 100mL double-neck round bottom flask, 50mL of dimethyl sulfoxide was added, stirred and heated to 140°C, and reacted for 12h After the reaction, the reaction solution was poured into 200 mL of water, and then extracted three times with dichloromethane to collect the organic phase; the dichloromethane in the organic phase was removed by distillation under reduced pressure, and finally dichloromethane and petroleum ether were used as developing agents to carry out silica gel. Column chromatography gave a yellow solid with a mass of 0.4 g (yield 57%);

The molar ratio of intermediate beta, basic salt and donor group D2 is ₁ :40:3.

Example 2

A preparation method of a diazobenzofluoranthene compound, comprising the steps:

In step S1, the molar ratio of 1,4-dibromo-2,3-difluorobenzene, fuming nitric acid and trifluoromethanesulfonic acid is 1:9:70, the nitration reaction temperature is 70°C, the reaction time is 24h, and the product The rate is 44%, and the others are the same as in Example 1.

In step S2, the molar ratio of 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene, iron powder and acetic acid is 1:15:175, the reduction reaction temperature is 40°C, and the reaction time is For 8h, the yield was 70%, and the others were the same as in Example 1.

In step S3, the molar ratio of 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine and acenaphthylenequinone compounds is 1:1, the condensation reaction temperature is 100°C, and the reaction time is 16h, The yield was 70%, and the others were the same as in Example 1.

In step S4, the molar ratio of the intermediate α, the basic salt, the palladium-containing coupling agent and the electron donor group D1 is ₁ :50:0.15:2.5, the heating reaction temperature is 180°C in a nitrogen atmosphere, and the reaction time is 12h, The yield was 70%, and the others were the same as in Example 1.

In step S5, the molar ratio of intermediate β, basic salt and donor group D2 is ₁ :50:4, the heating reaction temperature in nitrogen atmosphere is 100°C, the reaction time is 24h, the yield is 38%, and the other is the same. Example 1.

Example 3

A preparation method of a diazobenzofluoranthene compound, comprising the steps:

In step S1, the molar ratio of 1,4-dibromo-2,3-difluorobenzene, fuming nitric acid and trifluoromethanesulfonic acid is 1:8:45, the nitration reaction temperature is 50°C, the reaction time is 36h, and the yield is The rate is 72%, and the others are the same as in Example 1.

In step S2, the molar ratio of 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene, iron powder and acetic acid is 1:20:150, the reduction reaction temperature is 60°C, and the reaction time is For 6h, the yield was 80%, and the others were the same as in Example 1.

In step S3, the molar ratio of 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine to acenaphthylenequinone compound is 1:1, the condensation reaction temperature is 125°C, and the reaction time is 8h, The yield was 75%, and the others were the same as in Example 1.

In step S4, the molar ratio of the intermediate α, the basic salt, the palladium-containing coupling agent and the electron donor group D ₁ is 1:38:0.14:2.4, the heating reaction temperature is 100°C in a nitrogen atmosphere, and the reaction time is 24h, The yield was 80%, and the others were the same as in Example 1.

In step S5, the molar ratio of intermediate β, basic salt and donor group D ₂ is 1:35:3.5, the heating reaction temperature in nitrogen atmosphere is 150°C, the reaction time is 12h, and the yield is 50%. Others are the same as Example 1.

Example 4

A preparation method of a diazobenzofluoranthene compound, comprising the steps:

In step S1, the molar ratio of 1,4-dibromo-2,3-difluorobenzene, fuming nitric acid and trifluoromethanesulfonic acid is 1:7:40, and the yield is 70%, and the others are the same as in Example 1.

In step S2, the molar ratio of 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene, iron powder and acetic acid is 1:17:135, and the yield is 75%, and the other implementations are the same example 1.

In step S3, the molar ratio of 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine to acenaphthylenequinone compound is 1:0.8, the condensation reaction temperature is 125°C, and the reaction time is 12h, The yield was 80%, and the others were the same as in Example 1.

In step S4, the molar ratio of the intermediate α, the basic salt, the palladium-containing coupling agent and the electron donor group D ₁ is 1:35:0.13:2.2, the heating reaction temperature in a nitrogen atmosphere is 150°C, and the reaction time is 12h, The yield was 76%, and the others were the same as in Example 1.

In step S5, the molar ratio of intermediate β, basic salt and donor group D ₂ is 1:30:3, and the yield is 46%. Others are the same as in Example 1.

Example 5

A preparation method of a diazobenzofluoranthene compound, comprising the steps:

In step S1, the molar ratio of 1,4-dibromo-2,3-difluorobenzene, fuming nitric acid and trifluoromethanesulfonic acid is 1:6:50, and the yield is 65%, and the others are the same as in Example 1.

In step S2, the molar ratio of 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene, iron powder and acetic acid is 1:13:100, and the yield is 72%, and other implementations are the same as example 1.

In step S3, the molar ratio of 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine and acenaphthylenequinone compounds is 1:1.2, the condensation reaction temperature is 125°C, and the reaction time is 12h, The yield was 82%, and the others were the same as in Example 1.

In step S4, the molar ratio of intermediate α, basic salt, palladium-containing coupling agent and electron-donor group D1 is ₁ :30:0.11:2.1, and the yield is 72%. Others are the same as in Example 1.

In step S5, the molar ratio of intermediate β, basic salt and donor group D ₂ is 1:25:2.5, and the yield is 42%. Others are the same as in Example 1.

Example 6

A preparation method of a diazobenzofluoranthene compound, comprising the steps:

In step S1, the molar ratio of 1,4-dibromo-2,3-difluorobenzene, fuming nitric acid and trifluoromethanesulfonic acid was 1:6:45, and the yield was 60%, and the others were the same as in Example 1.

In step S2, the molar ratio of 1,4-dibromobenzene-2,3-difluoro-5,6-dinitrobenzene, iron powder and acetic acid is 1:10:120, and the yield is 70%, and other implementations are the same as example 1.

In step S3, the molar ratio of 3,6-dibromobenzene-4,5-difluoro-1,2-phenylenediamine and acenaphthylenequinone compounds is 1:1, the condensation reaction temperature is 125°C, and the reaction time is 12h, The yield was 87%, and the others were the same as in Example 1.

In step S4, the molar ratio of the intermediate α, the basic salt, the palladium-containing coupling agent and the electron donor group D1 is ₁ :25:0.1:2, and the yield is 68%, and the others are the same as in Example 1.

In step S5, the molar ratio of intermediate β, basic salt and donor group D ₂ is 1:20:2, and the yield is 40%. Others are the same as those in Example 1.

Example 7

A diazobenzofluoranthene compound, the structural formula is as follows:

The preparation method of the compound comprises the following steps:

Steps S1, S2 and S3 are the same as in Embodiment 1;

In step S4, the electron donor group D ₁ is triphenylamine-4-boronic acid (2.3eq), and others are the same as in Example 1;

In step S5, the electron donor group D ₂ is (4-(9-carbazolyl) phenylboronic acid (2.3eq), and the others are the same as in Example 1.

Example 8

A diazobenzofluoranthene compound, the structural formula is as follows:

The preparation method of the compound comprises the following steps:

Steps S1 and S2, others are the same as in Embodiment 1;

其他同实施例1；The structural formula of the acenaphthylene quinone compound in step S3 is

Others are the same as in Example 1;

In step S4, the electron donor group D ₁ is triphenylamine-4-boronic acid (2.3eq), and others are the same as in Example 1;

In step S5, the electron donor group D ₂ is (4-(9-carbazolyl) phenylboronic acid (2.3eq)), and the others are the same as in Example 1.

Example 9

A diazobenzofluoranthene compound, the structural formula is as follows:

The preparation method of the compound comprises the following steps:

Steps S1, S2 and S3 are the same as in Embodiment 1;

In step S4, the electron donor group D ₁ is 1,1'-bi-2-naphthol (1.2eq), and the others are the same as in Example 1;

In step S5, the electron donor group D ₂ is (4-(9-carbazolyl) phenylboronic acid (2.3eq)), and the others are the same as in Example 1.

result detection

Structural characterization and performance tests were performed on the diazobenzofluoranthene compounds prepared in Example 1 and Examples 7-9, respectively.

Specific test method:

(1) Compound structure detection

The diazobenzofluoranthene compounds prepared in Example 1 and Examples 7-9 were tested by Bruker's 400MHz superconducting nuclear magnetic resonance apparatus, and the solvent was deuterated chloroform.

(2) Mass spectrometry detection

The diazobenzofluoranthene compounds prepared in Example 1 and Example 7 were dissolved in acetonitrile, respectively, to prepare a solution with a concentration of 1 mg/mL, and the liquid mass spectrometer LCMS-2020 was used for testing.

(3) Ultraviolet absorption spectrum detection

Using Shimadzu UV-Vis spectrophotometer UV-2700, the diazobenzofluoranthene compounds prepared in Example 1 and Examples 7-9 were respectively dissolved in tetrahydrofuran (THF) solution to prepare 1×10 ^-3 mol. /L of the mother liquor, and then the mother liquor was diluted into a 1×10 ^-5 mol/L solution for testing, and the scanning range was 200-700 nm.

(4) Emission spectrum detection

Using steady-state/transient fluorescence spectrometer (FLS980), the diazobenzofluoranthene compounds prepared in Example 1 and Examples 7-9 were respectively dissolved in tetrahydrofuran (THF) solution to prepare 1×10 ^-3 mol. /L mother liquor, the mother liquor was diluted to 1×10 ^-5 mol/L solution and tested under nitrogen protection, the excitation wavelength was 314nm, and the test temperature was 300K.

(5) Fluorescence quantum yield detection

Using steady-state/transient fluorescence spectrometer (FLS980), the diazobenzofluoranthene compounds prepared in Example 1 and Examples 7-9 were respectively dissolved in toluene solution to prepare 1×10 ^-3 mol/L The mother liquor was diluted into a solution of 1×10 ^-5 mol/L and tested in an integrating sphere.

The test results are as follows:

The molecular hydrogen spectrum of the diazobenzofluoranthene compound in Example ¹ is shown in Figure ₂ , and it can be seen from the figure: 7.92, 7.91, 7.89, 7.70, 7.68, 7.54, 7.52, 7.50, 7.48, 7.40, 7.38, 7.37, 7.36, 7.23, 7.15, 7.12, 7.06, 7.04, 7.02, 7.00, 6.98, 6.96 The target products correspond one-to-one, and the quantity is reasonable; it can be seen from the mass spectrum (Fig. 3) that the relative molecular mass in Fig. 3 is 1066.35, plus one H, which is the same as the synthesized diazobenzofluoranthene compound in Example 1. The relative molecular mass is the same.

The molecular hydrogen spectrum of the diazobenzofluoranthene compound in Example ⁷ is shown in Figure ₄ , and it can be seen from the figure: 7.57, 7.55, 7.53, 7.52, 7.50, 7.46, 7.44, 7.42, 7.37, 7.35, 7.33, 7.12, 7.10, 7.08, 7.06, 7.04, 7.03, 7.01, the peak energy of molecular hydrogen spectrum corresponds to the target product one by one, and the number is reasonable ; It can be seen from the mass spectrum (Fig. 5) that the relative molecular mass in Fig. 5 is 1070.58, plus one H, which is consistent with the relative molecular mass of the synthesized diazobenzofluoranthene compound in Example 7.

The molecular hydrogen spectrum of the diazobenzofluoranthene compound in Example ₈ is shown in Figure ⁶ , and it can be seen from the figure: 7.33, 7.32, 7.30, 7.26, 7.25, 7.23, 7.21, 7.19, 7.18, 7.13, 7.11. The peaks of molecular hydrogen spectrum can correspond to the target product one by one, and the quantity is reasonable.

The molecular hydrogen spectrum _of the diazobenzofluoranthene compound in Example ⁹ is shown in Figure 7, and it can be seen from the figure: 7.91，7.89，7.86，7.85，7.65，7.64，7.56，7.55，7.53，7.48，7.46，7.45，7.40，7.39，7.37，7.32，7.31，7.30，7.25，7.24，7.22，7.02，7.00 It can correspond to the target product one by one, and the quantity is reasonable.

The ultraviolet-visible absorption spectrum of the diazobenzofluoranthene compound in 1×10 ⁻⁵ mol/L tetrahydrofuran in Example 1 is shown in FIG. 8 . As can be seen from the figure, the main absorption peak position of the diazobenzofluoranthene compound is 323 nm. The ultraviolet-visible absorption spectrum of the diazobenzofluoranthene compound in 1×10 ⁻⁵ mol/L tetrahydrofuran in Example 7 is shown in FIG. 9 . As can be seen from the figure, the main absorption peak position of the diazobenzofluoranthene compound is 325 nm.

The fluorescence emission spectrum of the diazobenzofluoranthene compound in Example 1 in 1×10 ⁻⁵ mol/L tetrahydrofuran is shown in FIG. 10 . As can be seen from the figure, the main emission peak position of the diazobenzofluoranthene compound is 531 nm. The fluorescence emission spectrum of the diazobenzofluoranthene compound in Example 2 in 1×10 ⁻⁵ mol/L tetrahydrofuran is shown in FIG. 11 . As can be seen from the figure, the main emission peak position of the diazobenzofluoranthene compound is 620 nm.

The absorption wavelength, emission wavelength, emission color and fluorescence quantum yield of the diazobenzofluoranthene compounds prepared in Example 1 and Examples 7 to 9 are shown in Table 1 for details.

Table 1 Absorption wavelength, emission wavelength and color and fluorescence quantum yield of diazobenzofluoranthene compounds

Numbering Absorption wavelength/nm Emission wavelength/nm glow color Fluorescence quantum yield Example 1 323 531 green light 96% Example 7 325 620 orange light 92% Example 8 340 713 near infrared light 89% Example 9 319 560 yellow light 90%

To sum up, the diazobenzofluoranthene compound provided by the present invention realizes long-wave emission, has the characteristics of tunable light color from green light to near-infrared light and fluorescence quantum yield, and can be used as a kind of compound with good performance and relatively low cost. Low new OLED light-emitting molecules. The diazobenzofluoranthene compound has significant economic value in applications such as preparing light-emitting materials, light-emitting devices or smart materials, and has good application prospects in the fields of full-color display and solid-state lighting. At the same time, the invention realizes the controllable preparation of the diazobenzofluoranthene compound, the preparation cost is low, the raw material sources are wide, the large-scale production can be realized, and the commercialization prospect is broad.

Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (3)

1. a diazobenzofluoranthene compound, is characterized in that, this compound is selected from any one in following structural formula:

2. diazide benzofluoranthene compound as claimed in claim 1, is characterized in that, the structural formula of this compound is:

3. The application of the diazobenzofluoranthene compound of claim 1 in the preparation of luminescent materials and smart materials.

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