CN107936013A - A kind of D π A π D type quinazolinone third order non-linear optical materials and its preparation method and application - Google Patents

Abstract

The object of the present invention is to provide the synthetic method of D π A π D type quinazolinone third order non-linear optical materials, this kind of compound is the good organic fluorescence materials of excellent in optical properties, stability.The present invention introduces triple carbon-carbon bonds using quinazolinone as precursor structure, in female ring and extends whole big pi-conjugated system, has obtained a kind of optical material for having preferable third-order non-linear response.The technical solution adopted by the present invention is：The present invention provides D π A π D type quinazolinone third order non-linear optical materials shown in a kind of formula (I)：In formula (I)：R is the alkoxy of hydrogen, halogen, the alkyl of C1 C4 or C1 C4.

Description

A kind of D-π-A-π-D type quinazolinone third-order nonlinear optical material and preparation method thereof law and application

(1) Technical field

The invention belongs to the technical field of new materials, and in particular relates to a D-π-A-π-D type quinazolinone third-order nonlinear optical material and its preparation method and application.

(2) Background technology

The 21st century is a high-speed information age. With the massive processing of information, people have higher and higher performance requirements for display and imaging devices, which greatly promotes the rapid development of optoelectronics. Therefore, nonlinear optical materials with special information processing functions and ultrafast response become the main body of future information material development. Different from inorganic nonlinear optical functional materials, organic nonlinear optical energy materials have the advantages of molecular design and tailoring, high response value, fast switching speed, high optical damage threshold, excellent mechanical strength, low dielectric constant, and good processing performance. The application of organic nonlinear optical materials mainly focuses on two aspects: one is to convert the frequency of light waves, that is, to broaden the range of laser wavelengths by means of frequency doubling, sum frequency, difference frequency or mixing, and optical parameter oscillation to open up new Laser light source. Second, it has great application potential in the fields of image processing, all-optical switches, optical storage and memory systems, etc. Therefore, designing and synthesizing new organic third-order nonlinear optical materials with excellent optical properties, thermal stability and processing properties is currently a very active research field.

The polarization of organic third-order nonlinear optical materials comes from the delocalization of π electrons on the main chain, the charges are easy to move, and the time required for the polarization of dielectric particles to generate electric dipoles is relatively short, showing strong photoelectric coupling characteristics. Some π-conjugated polymers have good electrochemical properties, photochemical properties, good mechanical properties and processing properties. Through reasonable modification of the molecular structure, the molecules show a large degree of delocalization, a large absorption wavelength, and a small The energy bandgap, the large molecular dipole moment, and the third-order nonlinear optical material with a higher third-order superization rate χ(3) are obtained. 11H pyrido[2,1-b]quinazol-11-one, structural formula Referred to as quinazolinone, due to the strong π-π interaction between its planar rigid skeleton molecules, it is easy to form molecular columns, and the molecular columns form layers through continuous intramolecular hydrogen bonds, and then form a three-dimensional structure from the layers. In addition, quinazolinones are widely used in chemical sensing, molecular assembly, and especially in the field of organic optoelectronics due to their large π-conjugated systems.

There is a close relationship between the electronic structure and geometric configuration of organic pigment molecules. It is generally believed that the third-order nonlinear optical properties are related to the delocalized large π conjugated structure in the molecule. Due to the highly conjugated large π structure of the parent ring and the multiple active sites that can be modified, quinazolinone derivatives, It has great application potential as a third-order nonlinear optical material. Combined with the design principles of third-order nonlinear optical materials, quinazolinones are modified to obtain quinazolinone third-order nonlinear optical materials with high response and strong photoelectric coupling characteristics.

(3) Contents of the invention

The object of the present invention is to provide a kind of D-π-A-π-D type quinazolinone third-order nonlinear optical material and its preparation method and application, the present invention according to the molecular structure characteristic of organic third-order nonlinear optical material, A series of organic fluorescent materials with excellent optical properties have been obtained by using quinazolinone as the parent ring and electron acceptor, and introducing carbon-carbon triple bonds into the parent ring to extend the entire large π-conjugated system.

The technical scheme adopted in the present invention is:

The invention provides a kind of D-π-A-π-D type quinazolinone third-order nonlinear optical material, characterized in that the D-π-A-π-D type quinazolinone third-order non-linear optical material is The structural formula of the linear optical material is shown in formula (I),

In formula (I): R is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy.

The second object of the present invention is to provide a method for synthesizing the above-mentioned D-π-A-π-D type quinazolinone third-order nonlinear optical material (compound shown in formula I), said synthetic method comprising the following steps :

(1) Ullmann reaction

Under the conditions of base A and copper catalyst A, 5-bromoisatin represented by formula (II) and 2,5-dibromopyridine in solvent A are subjected to Ullmann reaction at 90-150°C to obtain formula (III) The indicated dibromo compounds;

(2) Sonogashira coupling reaction

Under the protection of nitrogen, the dibrominated compound represented by formula (III) is added to solvent B, and under the action of alkali B, palladium catalyst A and copper catalyst B, it is mixed with phenylacetylene or substituted phenylacetylene at 60-100°C Carry out Sonogashira coupling reaction, obtain the quinazolinone derivative shown in formula (I);

In formula (I): R is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy

As a preference, the solvent A described in step (1) is N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, toluene or 1,4-dioxane, Alkali A is sodium bicarbonate, potassium hydroxide, sodium carbonate, potassium carbonate or cesium carbonate, copper catalyst A is cuprous chloride, cuprous bromide, cuprous iodide, copper oxide or copper acetate monohydrate, described The molar ratio of 5-bromoisatin represented by formula (II), 2,5-dibromopyridine, base A and copper catalyst A is 1:1～2:2～4:0.1～0.6, and the organic solvent The volumetric amount of A is 10-30 mL/g based on the mass of the quinazolinone represented by the formula (II).

Preferably, the solvent B in step (2) is tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene or 1,4-dioxane ; The palladium catalyst A is two (triphenylphosphine) palladium dichloride (PPh ₃ ) ₂ PdCl ₂ or four (triphenylphosphine) palladium Pd (PPh ₃ ) ₄ ; copper catalyst B is cuprous chloride , cuprous bromide or cuprous iodide; base B organic amines, preferably triethylamine, ethylenediamine or diisopropylamine; dibrominated compounds shown in the formula (III), phenylacetylene or substituted The molar ratio of phenylacetylene, palladium catalyst A and copper catalyst B is 1: 2～6: 0.05～0.3: 0.1～0.6; The volume consumption of described organic solvent B is represented by the dibrominated compound shown in formula (III) The mass is 20-50mL/g; the volume ratio of the base B to the organic solvent B is 2:1.

The third object of the present invention is to provide the application of the D-π-A-π-D quinazolinone third-order nonlinear optical material in fluorescent materials.

Beneficial effects of the present invention:

The invention introduces a phenylethynyl group with a substituent on the quinazolinone to expand the π-conjugated system of the molecule, reduces the energy band gap of the molecule, and makes the ultraviolet spectrum red-shift.

The synthetic D-π-A-π-D type quinazolinone third-order nonlinear optical material of the present invention has better thermal stability (TD (5%)>250 ℃), and electrochemical performance shows its HOMO/ The LUMO energy level difference is reduced, which is conducive to the transfer of intramolecular charges. The series of compounds have excellent third-order nonlinear optical properties, and have great potential in the application of nonlinear optical devices.

(4) Description of drawings

Fig. 1 is the ultraviolet-visible absorption spectrogram of quinazolinone mother ring and D-π-A-π-D type quinazolinone derivative (I) in dichloromethane prepared in embodiment 1-6.

Fig. 2 is the fluorescence spectrogram of the quinazolinone parent ring and D-π-A-π-D type quinazolinone derivative (I) prepared in Example 1-6 in dichloromethane.

Fig. 3 is the normalized opening Z scanning of quinazolinone parent ring and D-π-A-π-D type quinazolinone derivative (I) in dichloromethane prepared in embodiment 1-6 curve.

Fig. 4 is the normalized closed cell Z scanning of quinazolinone parent ring and D-π-A-π-D type quinazolinone derivative (I) in methylene chloride prepared in embodiment 1-6 curve.

(5) Specific implementation methods

The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:

Example 1

(1) Ullmann reaction

5-Bromoisatin (1.13g, 5mmol), 2,5-dibromopyridine (1.18mg, 5mmol), sodium bicarbonate (0.84g, 10mmol), and Cu(OAc) ₂ ·H ₂ O (0.10mg , 0.5mmol) was dissolved in 20mL DMF, stirred at 90°C for 24h, then the reaction was stopped, and the reaction solution was poured into 150mL saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V(dichloromethane)=2/1) to obtain 1.17 g of compound III as a yellow solid, with a yield of 67% (based on the amount of compound).

(2) Sonogashira coupling reaction

Under nitrogen protection, dibromocompound III (0.12g, 0.35mmol), cuprous iodide (0.0065g, 0.035mmol) and tetrakis (triphenylphosphine) palladium (0.021g, 0.0175mmol) were added to the three neck In the flask, 20 mL of anhydrous triethylamine and 10 mL of DMF were added under nitrogen. The reactant was first stirred at 80°C for 1 hour, then phenylacetylene (0.071g, 0.7mmol) was added dropwise to the reaction system, the temperature of the reaction solution was raised to 90°C, detected by TCL, and the reaction was stopped after stirring for 20 hours. After cooling, the reaction solution was poured into 30 mL of saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 1/1) to obtain a yellow The amount of quinazolinone derivative I-1 is 0.11 g, and the yield is 82% (based on the amount of the compound).

Example 2

(1) Ullmann reaction

5-Bromoisatin (1.13g, 5mmol), 2,5-dibromopyridine (1.42mg, 6mmol), potassium carbonate (1.38g, 10mmol), and CuI (0.19mg, 1mmol) were dissolved in 15mL DMSO, After stirring at 100° C. for 24 h, stop the reaction, pour the reaction solution into 150 mL of saturated brine, wait for the solid to be completely precipitated, filter, and the filter cake is purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 2/1) 0.91 g of compound III was obtained as a yellow solid, with a yield of 52% (based on the amount of compound).

(2) Sonogashira coupling reaction

Under nitrogen protection, dibromocompound III (0.12g, 0.35mmol), cuprous chloride (0.003g, 0.04mmol) and bis(triphenylphosphine) palladium dichloride (0.01g, 0.02mmol) were added Into a three-necked flask, add 20 mL of anhydrous diisopropylamine and 10 mL of 1,4-dioxane under nitrogen. The reactant was first stirred at 80°C for 1 hour, then p-methoxyphenylacetylene (0.28g, 2.10mmol) was added dropwise to the reaction system, the temperature of the reaction solution was raised to 90°C, detected by TCL, and the reaction was stopped after stirring for 20 hours. After cooling, the reaction solution was poured into 30 mL of saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 1/1) to obtain a yellow The amount of quinazolinone derivative I-2 is 0.13 g, and the yield is 79% (based on the amount of the compound).

Example 3

(1) Ullmann reaction

5-Bromoisatin (1.13g, 5mmol), 2,5-dibromopyridine (1.66mg, 7mmol), sodium carbonate (1.59g, 15mmol), and CuBr (0.14mg, 1mmol) were dissolved in 20mL 1,4 - in dioxane, after stirring at 90°C for 24h, stop the reaction, pour the reaction solution into 150mL saturated saline, wait for the solid to be completely precipitated, filter, and the filter cake is purified by silica gel column chromatography (V (petroleum ether)/ V (dichloromethane) = 2/1) to obtain 0.97 g of compound III as a yellow solid, with a yield of 55% (based on the amount of compound).

(2) Sonogashira coupling reaction

Under nitrogen protection, dibromocompound III (0.12g, 0.35mmol), cuprous bromide (0.03g, 0.21mmol) and tetrakis (triphenylphosphine) palladium (0.12g, 0.11mmol) were added to the three neck In the flask, add 20 mL of anhydrous ethylenediamine and 10 mL of DMSO under nitrogen. The reactant was first stirred at 80°C for 1 hour, and then p-chlorophenylacetylene (0.10 g, 0.7 mmol) was added dropwise to the reaction system. The temperature of the reaction solution was raised to 90° C., detected by TCL, and the reaction was stopped after stirring for 20 hours. After cooling, the reaction solution was poured into 30 mL of saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 1/1) to obtain a yellow The amount of quinazolinone derivative I-3 is 0.11 g, and the yield is 69% (based on the amount of the compound).

Example 4

(1) Ullmann reaction

5-bromoisatin (1.13g, 5mmol), 2,5-dibromopyridine (1.18mg, 5mmol), cesium carbonate (3.26g, 10mmol), and Cu(OAc) ₂ ·H ₂ O (0.20mg, 1mmol) was dissolved in 30mL toluene, stirred at 100°C for 24h, then the reaction was stopped, and the reaction solution was poured into 150mL saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether) /V (dichloromethane) = 2/1) to obtain 1.23 g of compound III as a yellow solid, with a yield of 70% (based on the amount of compound).

(2) Sonogashira coupling reaction

Under nitrogen protection, dibromocompound III (0.12g, 0.35mmol), cuprous chloride (0.02g, 0.21mmol) and bis(triphenylphosphine) palladium dichloride (0.07g, 0.11mmol) were added To a three-necked flask, add 20 mL of anhydrous diisopropylamine and 10 mL of THF under nitrogen. The reactant was first stirred at 80°C for 1 hour, then p-methylphenylacetylene (0.24g, 2.10mmol) was added dropwise to the reaction system, the temperature of the reaction solution was raised to 90°C, detected by TCL, and the reaction was stopped after stirring for 20 hours. After cooling, the reaction solution was poured into 30 mL of saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 1/1) to obtain a yellow The amount of quinazolinone derivative I-4 is 0.12 g, and the yield is 80% (based on the amount of the compound).

Example 5

(1) Ullmann reaction

Dissolve 5-bromoisatin (1.56 g, 5 mmol), 2,5-dibromopyridine (1.42 mg, 6 mmol), potassium hydroxide (0.56 g, 10 mmol), and CuCl (0.10 mg, 1 mmol) in 30 mL of DMF , after stirring at 150°C for 24h, the reaction was stopped, and the reaction solution was poured into 150mL saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) =2/1) 0.83 g of compound III was obtained as a yellow solid, with a yield of 47% (based on the amount of compound).

(2) Sonogashira coupling reaction

Under nitrogen protection, dibromocompound III (0.12g, 0.35mmol), cuprous iodide (0.03g, 0.18mmol) and bis(triphenylphosphine) palladium dichloride (0.02g, 0.04mmol) were added To a three-necked flask, add 20 mL of anhydrous triethylamine and 10 mL of DMA under nitrogen. The reactant was first stirred at 80°C for 1 hour, and then p-propylphenylacetylene (0.25 g, 1.75 mmol) was added dropwise to the reaction system. The temperature of the reaction solution was raised to 90° C., detected by TCL, and the reaction was stopped after stirring for 20 hours. After cooling, the reaction solution was poured into 30 mL of saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 1/1) to obtain a yellow The amount of quinazolinone derivative I-5 is 0.12 g, and the yield is 74% (based on the amount of the compound).

Example 6

(1) Ullmann reaction

5-Bromoisatin (1.13g, 5mmol), 2,5-dibromopyridine (2.37mg, 10mmol), sodium carbonate (2.12g, 20mmol), and CuO (0.24mg, 3mmol) were dissolved in 15mL DMSO, After stirring at 100° C. for 24 h, stop the reaction, pour the reaction solution into 150 mL of saturated brine, wait for the solid to be completely precipitated, filter, and the filter cake is purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 2/1) 0.9 g of compound III was obtained as a yellow solid, with a yield of 51% (based on the amount of compound).

(2) Sonogashira coupling reaction

Under nitrogen protection, dibromocompound III (0.12g, 0.35mmol), cuprous iodide (0.01g, 0.07mmol) and tetrakis (triphenylphosphine) palladium (0.04g, 0.04mmol) were added to the three neck In the flask, add 20 mL of anhydrous triethylamine and 10 mL of toluene under nitrogen. The reactant was first stirred at 80°C for 1 hour, and then p-butylphenylacetylene (0.17g, 1.05mmol) was added dropwise to the reaction system. The temperature of the reaction solution was raised to 90°C, detected by TCL, and stopped after stirring for 20 hours. After cooling, the reaction solution was poured into 30 mL of saturated brine, and the solid was completely precipitated, filtered, and the filter cake was purified by silica gel column chromatography (V (petroleum ether)/V (dichloromethane) = 1/1) to obtain a yellow The amount of quinazolinone derivative I-6 is 0.13 g, and the yield is 73% (based on the amount of the compound).

Example 7

The UV and Fluorescent Properties of Quinazolinone Mother Ring and Compound (I)

Wherein the quinazolinone parent ring structure is as follows:

Preparation of D-π-A-π-D type quinazolinone derivative (I) and quinazolinone parent ring in methylene chloride in the ultraviolet-visible absorption spectrum in methylene chloride is shown in accompanying drawing 1 in embodiment 1-6, The fluorescence spectrum in dichloromethane is shown in Figure 2: the compound was made into a solution with a concentration of 1×10 ^-5 M, the solvent was dichloromethane, and the instrument used was a Shimadzu UV-1800 spectrophotometer. The fluorescence correlation spectrum is shown in Figure 2: the compound was formulated into a solution with a concentration of 1×10 ^-6 M, the solvent was dichloromethane, and the instrument used was a Shimadzu RF-6000PC spectrometer. The test performance of (1) is as shown in table 1:

Table 1: Optical properties of D-π-A-π-D type quinazolinone derivatives (I)

Two prominent absorption features were observed in the spectra of I-1 to I-6 (Fig. 1). lower wavelength The bands for will be associated with the π-π* transitions of the benzene units in the molecule. higher wavelength The bands of may be related to the π-π* transition of the quinazolinone unit in the molecule. In contrast, compound I-2 shows a slight red shift, which has two reasons. On the one hand, when the strength of the electron donor increases, the absorption band of the molecule will red-shift, and the methoxyl group of I-2 is a stronger electron donating group. On the other hand, the lone pair of electrons of the oxygen atom and the π electrons of the double bond form an effective p-π conjugation. The parent ring has an absorption maximum at 354 nm. Obviously, the λabs of I-1~I-6 are significantly red-shifted compared with the parent ring, which reflects the effect of extended π conjugation, which is caused by the integration of phenylacetylene bonds. UV-Vis absorption spectra showed that the functional groups on quinazolinones would affect the ground state and excited state of the molecule, and specific functional groups could be introduced at multiple active sites to adjust the photophysical properties of the compound.

The fluorescence emission spectrum (Figure 2) has a consistent change trend with the UV absorption spectrum, and compound I-2 shows a slight red shift, which is due to the effective p-π co-existence of the lone pair of electrons of the oxygen atom and the π electrons of the double bond. yoke. The fluorescence emission wavelength of the parent ring is about 440 nm, showing strong blue fluorescence. Apparently, the λems of the disubstituted quinazolinone derivatives I-1∼I-6 showed significant red-shifts because of the integration of phenylethynyl bonds caused by π-conjugation extension.

Example 8

Third-Order Nonlinear Detection of Quinazolinone Mother Ring and Compound (I)

Wherein the quinazolinone parent ring structure is as follows:

The D-π-A-π-D type quinazolinone derivative (I) prepared in embodiment 1-6 and the normalized opening Z-scan curve of the quinazolinone parent ring in dichloromethane are shown in the appendix Figure 3. The normalized closed-cell Z-scan curve in dichloromethane is shown in Figure 4: We used the Z-scan technique to test the third-order nonlinearity. The sample was made into a dichloromethane solution with a concentration of 1×10 ^-5 M, and placed in a sample cell with a thickness of 2mm. The laser pulse energy used in the experiment was 0.1uJ, the wavelength was 532nm, and the pulse width was 120fs. The beam waist radius of the spot is 30um. Before testing the samples, the nonlinear optical effect of the solvent dichloromethane was tested under the same conditions, and it was found that there was no nonlinear absorption. Therefore, the influence of the nonlinear optical effect of the solvent on the test can be ignored.

Figure 3 shows the normalized signals of quinazolinone derivatives measured under open-pore conditions, which are used to describe the absorption process of third-order nonlinear optics. The small black circles are the experimental data, and the red solid line is fit the curve. All the compounds show anti-saturated absorption curves symmetrical about the focal point (Z=0), and the samples have the lowest transmission intensity at the focal point.

When the nonlinear absorption exists, a curve of the open hole and a closed hole is made respectively, and the data measured under the closed hole is divided by the data of the open hole to obtain a single nonlinear refraction property after normalization. Through this data processing, the nonlinear refractive properties of D-π-A-π-D quinazolinone derivatives were obtained, as shown in FIG. 4 . It can be seen from Figure 4 that all graphs appear in the shape of a valley first and then a peak, indicating that the nonlinear refraction coefficient n2>0 is a self-focusing phenomenon, and the difference between the peak and the trough (ΔTp-v) and the third-order nonlinear refraction The coefficient n2(m2/W) is related.

The third-order nonlinear optical material properties are evaluated by the value of the third-order nonlinear polarization coefficient χ ⁽³⁾ . The larger the value of the third-order nonlinear polarization coefficient χ ⁽³⁾ , the better the third-order nonlinear performance of the material.

NLO parameters were calculated according to Eq. and summarized in Table 2.

where n ₀ is the linear refractive index of the solvent methylene chloride, ω is the angular frequency of the light field, N is the number density of molecules per cubic centimeter, and F is the local field correction factor equal to (n ₀ ² +2)/3.

Table 2: Third-order nonlinear parameters of D-π-A-π-D quinazolinone derivatives (I)

In Table 2, χ ⁽³⁾ is the third-order nonlinear susceptibility of the material, which is a macroscopic polarization effect parameter, which is related to the concentration of the measured material and reflects the relationship between molecules and molecules; γ is the material’s Molecular second-order hyperpolarizability is a microscopic polarization effect parameter, which has nothing to do with the concentration of the measured material. It does not reflect the relationship between molecules and molecules, and can better explain the nonlinear effect at the molecular microstructure level. Both are important indicators to characterize the third-order nonlinear optical properties of material molecules at the microscopic level.

The data in Figure 3 and Table 2 clearly show that the third-order nonlinear susceptibility χ ⁽³⁾ of compounds I-1～I-6 is 1.2～3.0 times that of the parent ring, and the molecular second-order hyperpolarizability γ is The female ring is 2.8 to 7.0 times. This is because the intramolecular charge transfer efficiency to the entire quinazolinone structure is significantly enhanced by extending the π-conjugated system. At the same time, because the oxygen atom of the methoxy group on the benzene ring on both sides of the molecule of compound I-2 can form an effective p-π conjugation with the benzene ring and the entire large π conjugated system, it can be combined with the quinazolinone with electro-absorbing properties. The parent ring forms an electron-donating system and thus has a higher third-order nonlinear response than several other compounds. In summary, the quinazolinone derivatives designed and synthesized by the present invention are a class of potential third-order nonlinear optical materials.

The above only lists preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereto. Any changes made by those skilled in the art within the scope of the claims of the present invention all fall within the protection scope of the present invention.

Claims (6)

1. A D-π-A-π-D type quinazolinone third-order nonlinear optical material, characterized in that, the D-π-A-π-D type quinazolinone third-order nonlinear The structural formula of the optical material is shown in formula (I), In formula (I): R is hydrogen, halogen, C1-C4 alkyl or C1-C4 alkoxy. 2. a kind of D-π-A-π-D type quinazolinone third-order nonlinear optical material according to claim 1, is characterized in that, described D-π-A-π-D type quinazolinone The structural formula of the third-order nonlinear optical material of oxazolinone is preferably as follows: 3. a method for preparing D-π-A-π-D type quinazolinone third-order nonlinear optical material as claimed in claim 1, is characterized in that, described preparation method comprises the steps: (1) Ullmann reaction Under the conditions of base A and copper catalyst A, 5-bromoisatin represented by formula (II) and 2,5-dibromopyridine in solvent A are subjected to Ullmann reaction at 90-150°C to obtain formula (III) The indicated dibromo compounds; (2) Sonogashira coupling reaction Under the protection of nitrogen, the dibrominated compound represented by formula (III) is added to solvent B, and under the action of alkali B, palladium catalyst A and copper catalyst B, it is mixed with phenylacetylene or substituted phenylacetylene at 60-100°C Carry out Sonogashira coupling reaction, obtain the quinazolinone derivative shown in formula (IV); 4. D-π-A-π-D type quinazolinone optical material preparation method as claimed in claim 3, is characterized in that, solvent A described in step (1) is N,N-dimethyl formaldehyde Amide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene or 1,4-dioxane, base A is sodium bicarbonate, potassium hydroxide, sodium carbonate, potassium carbonate or cesium carbonate, copper Catalyst A is cuprous chloride, cuprous bromide, cuprous iodide, copper oxide or copper acetate monohydrate, 5-bromoisatin shown in the described formula (II), 2,5-dibromopyridine, The molar ratio of alkali A and copper catalyst A is 1:1～2:2～4:0.1～0.6, and the volume consumption of described organic solvent A is calculated by the mass of 5-bromoisatin shown in formula (II) 10～30mL/g. 5. D-π-A-π-D type quinazolinone optical material preparation method as claimed in claim 3, is characterized in that, step (2) described solvent B is THF, N,N-dimethyl Formamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene or 1,4-dioxane; the palladium catalyst A is bis(triphenylphosphine)palladium dichloride (PPh ₃ ) ₂ PdCl ₂ or tetrakis (triphenylphosphine) palladium Pd (PPh ₃ ) ₄ ; copper catalyst C is cuprous chloride, cuprous bromide or cuprous iodide; base B organic amines, preferably triethyl Amine, ethylenediamine or diisopropylamine; the molar ratio of the dibrominated compound represented by the formula (III), phenylacetylene or substituted phenylacetylene, palladium catalyst A and copper catalyst B is 1:2 to 6:0.05 ～0.3: 0.1～0.6; The volume consumption of described organic solvent C is 20～50mL/g by the mass of the dibrominated compound shown in formula (III); The volume consumption of described alkali B is the same as that of organic solvent B The volume to dosage ratio is 2:1. 6. The application of the D-π-A-π-D type quinazolinone third-order nonlinear optical material in claim 1 in nonlinear optical devices.