CN106699763A - Chemical compound taking quinazolinone derivative as core and application of chemical compound - Google Patents

Abstract

The invention discloses a compound with quinazolinone derivatives as the core and its application in organic electroluminescent devices. It has the characteristics of good film-forming properties. When the compound of the present invention is used as a light-emitting layer material of an OLED light-emitting device, the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the life of the device is significantly improved.

Description

A kind of compound with quinazolinone derivative as core and application thereof

technical field

The invention relates to the technical field of semiconductors, in particular to a compound of a quinazolinone derivative and its application as a light-emitting layer material in an organic light-emitting diode.

Background technique

Organic electroluminescent (OLED: Organic Light Emission Diodes) device technology can be used to manufacture new display products and also can be used to make new lighting products, which is expected to replace the existing liquid crystal display and fluorescent lighting, and has a wide application prospect.

The OLED light-emitting device is like a sandwich structure, including electrode material film layers, and organic functional materials sandwiched between different electrode film layers. Various functional materials are superimposed on each other according to the application to form an OLED light-emitting device. As a current device, when a voltage is applied to the electrodes at both ends of the OLED light-emitting device, and the positive and negative charges in the organic layer functional material film are acted on by the electric field, the positive and negative charges are further recombined in the light-emitting layer, that is, OLED electroluminescence is generated.

The application of organic light-emitting diodes (OLEDs) in large-area flat-panel displays and lighting has attracted extensive attention from both industry and academia. However, traditional organic fluorescent materials can only use 25% of the singlet excitons formed by electrical excitation to emit light, and the internal quantum efficiency of the device is low (up to 25%). The external quantum efficiency is generally lower than 5%, and there is still a big gap with the efficiency of phosphorescent devices. Although phosphorescent materials enhance intersystem crossing due to the strong spin-orbit coupling at the center of heavy atoms, the singlet and triplet excitons formed by electrical excitation can be effectively used to emit light, so that the internal quantum efficiency of the device can reach 100%. However, phosphorescent materials are expensive, poor material stability, serious device efficiency roll-off and other problems limit their application in OLEDs. Thermally activated delayed fluorescence (TADF) materials are the third-generation organic light-emitting materials developed after organic fluorescent materials and organic phosphorescent materials. This type of material generally has a small singlet-triplet energy level difference (△E _ST ), and the triplet excitons can be transformed into singlet excitons to emit light through anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation, and the internal quantum efficiency of the device can reach 100%. At the same time, the structure of the material is controllable, the properties are stable, the price is cheap and no precious metals are required, and the application prospects in the field of OLEDs are broad.

Although theoretically TADF materials can achieve 100% exciton utilization, there are actually the following problems: (1) The T1 and S1 states of the designed molecules have strong CT characteristics, and the very small S1-T1 state energy gap, although it can A high T ₁ → S ₁ state exciton conversion rate is achieved through the TADF process, but at the same time it leads to a low S1 state radiative transition rate. Therefore, it is difficult to achieve both (or simultaneously) high exciton utilization efficiency and high fluorescence radiation efficiency; (2 ) Even if doped devices have been used to alleviate the quenching effect of T exciton concentration, most devices made of TADF materials have a serious efficiency roll-off at high current densities.

As far as the actual needs of the current OLED display lighting industry are concerned, the development of OLED materials is far from enough and lags behind the requirements of panel manufacturers. It is particularly important for material companies to develop higher-performance organic functional materials.

Contents of the invention

In view of the above-mentioned problems in the prior art, the applicant provides a compound with quinazolinone derivatives as the core and its application in organic electroluminescent devices. The compound of the invention is derived from quinazolinone as the core, and is used as a light-emitting layer material in an organic light-emitting diode. The device produced by the invention has good photoelectric performance and can meet the requirements of panel manufacturers.

Technical scheme of the present invention is as follows:

The applicant provides a kind of compound with quinazolinone derivative as the core, said compound structure is as shown in general formula (1):

In the general formula (1), Ar ₁ and Ar ₂ independently represent or -R;

Wherein, Ar represents the aryl group of C _5-20 ; n takes 1 or 2;

R selects hydrogen or the structure shown in general formula (2), and at least one of R in Ar ₁ and Ar ₂ selects the structure shown in general formula (2):

In the general formula (2), R ₁ and R ₂ are independently selected from hydrogen, C _1-10 straight chain or branched chain alkyl, C _5-20 cycloalkyl, C _5-20 aryl, C _{5 -20} heteroaryl or structure shown in general formula (3);

In general formula (3), R ₃ and R ₄ are independently selected from C _1-10 straight chain or branched chain alkyl, C _5-20 cycloalkyl, C _5-20 aryl or C _5-20 heteroaryl.

Preferably, R1 and R2 in the general formula (2) independently select the structure shown in the general formula (4), general formula (5) or general formula (6):

Wherein, X described in general formula (5) and general formula (6) represents oxygen atom, sulfur atom, selenium atom, C _1-10 linear or branched chain alkylene substituted alkylene, aryl substituted alkylene One of alkyl, alkyl or aryl substituted secondary amino groups.

Preferably, R in the general formula (1) is:

any of the.

Preferably, the specific structural formula of the compound is:

any of the.

The applicant also provides a light-emitting device comprising the compound, and the compound is used as a light-emitting layer material for making an OLED device.

The applicant also provides a method for preparing the compound, the reaction equation occurring in the preparation process is:

In the reaction formulas 1-2, X each independently represents Cl, Br, or I;

n and m are independently represented as 0 or 1;

Wherein the preparation method of reaction formula 1 is:

Weigh quinazolinone halides, Ar ₁ -H, Ar ₂ -H, and dissolve them in toluene; then add Pd ₂ (dba) ₃ , tri-tert-butylphosphine, and sodium tert-butoxide; under an inert atmosphere, place The mixed solution of the above reactants is reacted at a reaction temperature of 95-110°C for 10-24 hours, cooled and filtered the reaction solution, the filtrate is rotary evaporated, and passed through a silica gel column to obtain the target product;

The molar ratio of the halogenated quinazolinone to Ar ₁ -H and Ar ₂ -H is 1:0.8～2.0:0.8～2.0, and the molar ratio of Pd ₂ (dba) ₃ to the halogenated quinazolinone 0.006～0.02:1, the molar ratio of tri-tert-butylphosphine to the halogenated quinazolinone is 0.006～0.02:1, and the molar ratio of sodium tert-butoxide to the halogenated quinazolinone is 1.0～3.0: 1;

The preparation method of reaction formula 2 is:

Weigh the halides of quinazolinone, Ar ₁ -B(OH) ₂ , Ar ₂ -B(OH) ₂ , and dissolve them in a mixed solvent of toluene and ethanol with a volume ratio of 2:1; under an inert atmosphere, add Na ₂ CO ₃ aqueous solution, Pd(PPh ₃ ) ₄ ; react the mixed solution of the above reactants at a reaction temperature of 95-110°C for 10-24 hours, cool and filter the reaction solution, spin the filtrate, and pass it through a silica gel column to obtain the target product ;

The molar ratio of the halogenated quinazolinone to Ar ₁ -B(OH) ₂ and Ar ₂ -B(OH) ₂ is 1:1.0～2.0:1.0～2.0; Na ₂ CO ₃ and quinazoline The molar ratio of the halogenated ketone is 1.0-3.0:1; the molar ratio of Pd(PPh ₃ ) ₄ to the halogenated quinazolinone is 0.006-0.02:1.

The beneficial technical effects of the present invention are:

The combination of electron donor (donor, D) and electron acceptor (acceptor, A) in the structure molecule of the compound of the present invention can increase orbital overlap, improve luminous efficiency, and connect aromatic heterocyclic groups to obtain HOMO and LUMO space separation. The material in the charge transfer state realizes a small energy level difference between the S1 state and the T1 state, thereby realizing reverse intersystem crossing under thermal stimulation conditions. The compound uses quinazoline derivatives as the mother nucleus and connects aromatic groups. It destroys the crystallinity of molecules and avoids the aggregation between molecules. Most of the molecules are rigid groups, which have good film-forming properties and fluorescence quantum efficiency, and are suitable for use as doping materials for the light-emitting layer; the internal trivalent of quinolinone The nitrogen atom is a saturated atom, which not only has strong rigidity, but also helps to increase the triplet energy level of the mother nucleus compound. The combination of electron donor and electron acceptor can increase the mobility of electrons and holes, reduce the starting voltage, and improve Exciton recombination efficiency improves device performance.

The compound described in the present invention can be used as a light-emitting layer material in the production of OLED light-emitting devices, and good device performance is obtained, and the current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; at the same time, the life of the device is significantly improved. The compound material of the invention has a good application effect in OLED light-emitting devices and has a good industrialization prospect.

Description of drawings

Fig. 1 is the device structure schematic diagram using the compound of the present invention;

Among them, 1 is the transparent substrate layer, 2 is the ITO anode layer, 3 is the hole injection layer, 4 is the hole transport layer, 5 is the light emitting layer, 6 is the electron transport layer, 7 is the electron injection layer, and 8 is the cathode reflective electrode Floor.

detailed description

The synthesis of embodiment 1 compound 3

In a 250ml four-neck flask, add 0.01mol 3-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one, 0.015mol Compound B1, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 150ml toluene, heated to reflux for 24 hours, sampled and plated, the reaction was complete, Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 97.36% and a yield of 65.4%.

HPLC-MS (m/z): theoretical value 761.32, found value 761.42.

The synthesis of embodiment 2 compound 4

In a 250ml four-neck flask, add 0.01mol 3-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one, 0.015mol Compound B2, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 150ml toluene, heated to reflux for 24 hours, sampled and plated, the reaction was complete, Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 96.59% and a yield of 69.8%.

HPLC-MS (m/z): theoretical value 817.38, found value 817.65.

The synthesis of embodiment 3 compound 10

In a 500ml four-neck flask, under nitrogen atmosphere, add 0.01mol 2-bromo-benzo[d]benzo[4,5]imidazo[2,1-b]oxazole, 0.015mol compound C1, and use Dissolve the mixed solvent (180ml toluene, 90ml ethanol), then add 0.03mol Na ₂ CO ₃ aqueous solution (2M), then add 0.0001mol Pd(PPh ₃ ) ₄ , heat and reflux for 10-24 hours, take a sample and spot the plate, and the reaction is complete. Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with an HPLC purity of 97.80% and a yield of 69.50%.

HPLC-MS (m/z): The theoretical value is 837.35, and the measured value is 837.69.

The synthesis of embodiment 4 compound 23

In a 500ml four-neck flask, under nitrogen atmosphere, add 0.01mol 2-bromo-benzo[d]benzo[4,5]imidazo[2,1-b]oxazole, 0.015mol compound C1, and use Dissolve the mixed solvent (180ml toluene, 90ml ethanol), then add 0.03mol Na ₂ CO ₃ aqueous solution (2M), then add 0.0001mol Pd(PPh ₃ ) ₄ , heat and reflux for 10-24 hours, take a sample and spot the plate, and the reaction is complete. Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with an HPLC purity of 97.20% and a yield of 67.50%.

HPLC-MS: material value 837.35, found 837.65.

The synthesis of embodiment 5 compound 30

In a 250ml four-necked flask, under a nitrogen atmosphere, add 0.01mol 8-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one, 0.015mol Compound B1, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 150ml toluene, heated to reflux for 24 hours, sampled and plated, the reaction was complete, Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 98.75% and a yield of 56.29%.

HPLC-MS (m/z): theoretical value 761.32, found value 761.89.

The synthesis of embodiment 6 compound 31

In a 250ml four-neck flask, add 0.01mol 0.01mol 8-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one under nitrogen atmosphere, 0.015 mol of compound B2, 0.03 mol of sodium tert-butoxide, 1×10 ^-4 mol of Pd ₂ (dba) ₃ , 1×10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heat and reflux for 24 hours, sample and spot the plate, and react complete, naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 99.25% and a yield of 58.12%.

HPLC-MS (m/z): theoretical value 817.38, found value 817.65.

The synthesis of embodiment 7 compound 33

In a 250ml four-neck flask, add 0.01mol 0.01mol 8-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one under nitrogen atmosphere, 0.015mol of compound B3, 0.03mol of sodium tert-butoxide, 1×10 ^-4 mol of Pd ₂ (dba) ₃ , 1×10 ^-4 mol of tri-tert-butylphosphine, 150ml of toluene, heat and reflux for 24 hours, take a sample and spot the plate, and react complete, naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 99.25% and a yield of 58.12%.

HPLC-MS (m/z): theoretical value 985.57, found value 985.78.

The synthesis of embodiment 8 compound 35

In a 500ml four-neck flask, under nitrogen atmosphere, add 0.01mol 2-bromo-benzo[d]benzo[4,5]imidazo[2,1-b]oxazole, 0.015mol compound C1, and use Dissolve the mixed solvent (180ml toluene, 90ml ethanol), then add 0.03mol Na ₂ CO ₃ aqueous solution (2M), then add 0.0001mol Pd(PPh ₃ ) ₄ , heat and reflux for 10-24 hours, take a sample and spot the plate, and the reaction is complete. Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with an HPLC purity of 97.20% and a yield of 67.50%.

HPLC-MS (m/z): theoretical value 837.35, found value 837.39.

The synthesis of embodiment 9 compound 58

In a 250ml four-neck flask, add 0.01mol 3-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one, 0.015mol Compound B4, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 150ml toluene, heated to reflux for 24 hours, sampled and plated, the reaction was complete, Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 97.60% and a yield of 46.00%.

HPLC-MS (m/z): The theoretical value is 993.44, and the measured value is 992.89.

The synthesis of embodiment 10 compound 59

In a 250ml four-neck flask, add 0.01mol 3-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one, 0.015mol Compound B5, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 150ml toluene, heated to reflux for 24 hours, sampled and plated, the reaction was complete, Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 99.25% and a yield of 49.00%.

HPLC-MS (m/z):; theoretical value 941.34, found value 940.98.

The synthesis of embodiment 11 compound 62

In a 250ml four-neck flask, under a nitrogen atmosphere, add 0.01mol 8-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one, 0.020mol Compound B6, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 150ml toluene, heated to reflux for 24 hours, sampled and plated, the reaction was complete, Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 95.62% and a yield of 32.15%.

HPLC-MS (m/z): theoretical value 811.37, found value 811.89.

The synthesis of embodiment 12 compound 78

In a 250ml four-necked flask, add 0.01mol 3,8-dibromo-6,6-dimethylindolo[2,1-B]quinazolin 12(6H)-one under nitrogen atmosphere , 0.03mol carbazole, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 250ml toluene, heated to reflux for 24 hours, sampling plate, The reaction was complete, cooled naturally, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 95.16% and a yield of 29.70%.

HPLC-MS (m/z): theoretical value 592.23, found value 593.12.

The synthesis of embodiment 13 compound 86

In a 250ml four-necked flask, add 0.01mol 2,8-dibromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one under nitrogen atmosphere , 0.015mol raw material D, 0.03mol sodium tert-butoxide, 1×10-4mol Pd ₂ (dba) ₃ , 1×10-4mol tri-tert-butylphosphine, 250ml toluene, heat and reflux for 24 hours, take a sample point plate, the reaction is complete , cooled naturally, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 98.86 and a yield of 35.70%.

HPLC-MS (m/z): theoretical value 592.23, found value 592.65.

The synthesis of embodiment 14 compound 104

In a 500ml four-neck flask, under an atmosphere of nitrogen gas, add 0.01mol 2-bromo-benzo[d]benzo[4,5]imidazol[2,1-b]oxazole, 0.015mol compound C2, and use Dissolve the mixed solvent (180ml toluene, 90ml ethanol), then add 0.03mol Na ₂ CO ₃ aqueous solution (2M), then add 0.0001mol Pd(PPh ₃ ) ₄ , heat and reflux for 10-24 hours, take a sample and spot the plate, and the reaction is complete. Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with an HPLC purity of 97.80% and a yield of 69.50%.

HPLC-MS (m/z): theoretical value 837.35, found value 838.45.

The synthesis of embodiment 15 compound 115

In a 500ml four-neck flask, under nitrogen atmosphere, add 0.01mol 8-bromo-6,6-dimethylindolo[2,1-b]quinazolin 12(6H)-one, 0.015mol Compound B7, 0.03mol sodium tert-butoxide, 1×10 ^-4 mol Pd ₂ (dba) ₃ , 1×10 ^-4 mol tri-tert-butylphosphine, 250ml toluene, heated to reflux for 24 hours, sampled and plated, the reaction was complete, Naturally cooled, filtered, the filtrate was rotary evaporated, and passed through a silica gel column to obtain the target product with a purity of 98.86 and a yield of 35.70%.

HPLC-MS (m/z): theoretical value 789.35, found value 789.63.

The compounds of the present invention can be used as doping or auxiliary host materials for the light-emitting layer. Compound 3, Compound 4, Compound 10, Compound 30, Compound 31, Compound 33, Compound 58, Compound 59, Compound 104, Compound 115 and the prior art The thermal properties, △Est and Φf of the commonly used BD-1 materials were measured respectively, and the test results are shown in Table 1.

Table 1

Note: The thermogravimetric temperature Td is the temperature at which 1% of the weight is lost in a nitrogen atmosphere. It is measured on the TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, and the nitrogen flow rate is 20mL/min; Tg is measured by the DSC-60 of Shimadzu Corporation. The thermal difference scanning analyzer is measured, and the nitrogen flow rate is 10mL/min; △Est is the fluorescence emission spectrum and the phosphorescence emission spectrum of the test compound respectively, and is calculated from the fluorescence emission peak and the phosphorescence emission peak (testing equipment: using the FLS980 of Edinburgh Instruments Fluorescence spectrometer, Optistat DN-V2 low-temperature component of Oxford Instruments); Φf is the solid powder fluorescence quantum efficiency (Using the Maya2000Pro fiber optic spectrometer of Ocean Optics of the United States, the C-701 integrating sphere of Lanfei Company of the United States and the LLS-LED light source of Ocean Optics Test the solid fluorescence quantum efficiency test system, and measure it with reference to the method of document Adv.Mater.1997, 9, 230-232).

In order to better evaluate the applicability of the compounds of the present invention as doping materials and auxiliary host materials, the compounds of the present invention and existing materials mCP, BD-1, and RD-1 were subjected to the following organic film fluorescence quantum efficiency and lifetime experiments:

1. Using mCP as the main material, the compound of the present invention and the existing material BD-1 are respectively used as doping materials (5wt%);

2. Using mCP as the main material (85wt%), the compound of the present invention and the existing material BD-1 are respectively used as the auxiliary main material (15wt%), and RD-1 is used as the doping material (4wt%);

The above-mentioned organic film is irradiated with ultraviolet light of 365 nm, and the fluorescence quantum efficiency (PLQY) of the organic film is measured; meanwhile, LT50 (the time for the luminous brightness to decay to 50% of the initial brightness) is measured. The test results are shown in Table 2:

Table 2

Organic film (15nm) QUR LT50 mCP: Compound 3 (4wt%) 92% 5.9h mCP: compound 10 (4wt%) 90% 6.4h mCP: compound 30 (4wt%) 91% 4.9h mCP: compound 33 (4wt%) 88% 6.8h mCP: BD-1 (4wt%) 68% 3.5h mCP: Compound 3: RD-1 (85:15:4) 76% 5.4h mCP:Compound 10:RD-1(85:15:4) 75% 4.9h mCP:Compound 30:RD-1(85:15:4) 80% 5.2h mCP:Compound 33:RD-1(85:15:4) 72% 4.5h mCP:BD-1:RD-1 (85:15:4) 58% 3.0h

Note: The organic film is co-evaporated with two sources by ANS evaporation equipment, and the evaporation substrate is high-transmittance quartz glass. After the evaporation is completed, the packaging is carried out in a glove box (the concentration of water and oxygen is less than 1ppm). PLQY (absolute fluorescence quantum efficiency) adopts the Japanese HAMAMAT (C11347-11Quantaurus-QY) test system; LT50 adopts the OLED lifetime test system of Shanghai University.

From the data in the above table, it can be seen that the compound of the present invention has a relatively low △E _st , and it is easy to achieve a high T ₁ → S ₁ state exciton conversion rate, and is suitable as an auxiliary host material for the light-emitting layer; the compound of the present invention also has relatively high Φf and The higher radiation transition rate of the S1 state improves the efficiency and lifespan of the OLED device using the compound of the invention as a dopant material.

The HOMO and LUMO energy levels of the compounds of the present invention are calculated and visualized by the ab initio calculation software ORCA of quantum chemistry, and the calculation method adopts B3LYP hybrid functional, basis set 6-31g(d). The visualized HOMO and LUMO distributions of compound 10, compound 23, compound 35 and compound BD-1 are shown in Table 3;

From the spatial distribution of HOMO and LUMO in the molecule, it can be seen that the HOMO and LUMO energy levels of the compound of the present invention are in a state of spatial separation, and the overlapping degree of HOMO and LUMO is small, resulting in a small singlet-triplet energy level difference, which is beneficial to the triplet state. Excitons are transformed into singlet excitons through thermal excitation, which theoretically enables the quantum efficiency of the device to reach 100%.

table 3

The application effects of the compound synthesized in the present invention as the dopant material of the light-emitting layer in the device are described in detail below through Examples 16-23 and Comparative Example 1. Compared with Comparative Example 1 in Examples 16-23, the material of the light-emitting layer of the device described in Comparative Example 1 uses existing commonly used raw materials, while the dopant material of the light-emitting layer of the device in Examples 16-23 uses the compound of the present invention. The structural composition of the devices obtained in each embodiment is shown in Table 4. The performance test results of each device are shown in Table 5.

Comparative example 1

The transparent glass substrate 1 is made of transparent material. The ITO anode layer 2 (with a film thickness of 150nm) was washed, that is, alkali washing, pure water washing, drying, and then ultraviolet-ozone washing to remove organic residues on the transparent ITO surface. Concrete preparation process is as follows:

On the ITO anode layer 2 after the above-mentioned cleaning, HAT-CN was evaporated with a film thickness of 10 nm by using a vacuum evaporation device, and this layer of organic material was used as the hole injection layer 3 . Next, TAPC (4,4′,4″-tris(carbazol-9-yl)triphenylamine) was vapor-deposited with a thickness of 70 nm as the hole transport layer 4 .

After the evaporation of the above-mentioned hole transport material is completed, the light-emitting layer 5 of the OLED light-emitting device is produced, and its structure includes the material mCP used in the OLED light-emitting layer 5 as the host material, and BD-1 as the doping material, and the doping ratio is 4% by weight , the film thickness of the light-emitting layer is 25nm.

After the above-mentioned light-emitting layer 5, continue to vacuum evaporate the electron transport layer material to be TPBI. The vacuum-evaporated film thickness of this material is 35 nm, and this layer is the electron transport layer 6 .

On the electron transport layer 6, a lithium fluoride (LiF) layer with a film thickness of 1 nm was formed by a vacuum evaporation device, and this layer was the electron injection layer 7 .

On the electron injection layer 7, an aluminum (Al) layer with a film thickness of 80 nm was formed by a vacuum evaporation device, and this layer was used for the cathode reflective electrode layer 8. The material structure of each layer is as follows:

The structure of the manufactured OLED light-emitting device is shown in Table 4, and the test results are shown in Table 5.

After the OLED light-emitting device is manufactured as described above, the anode and the cathode are connected with a known driving circuit to measure the luminous efficiency, luminous color and device life of the device (LT95: brightness decays to 95% of the initial brightness).

Example 16

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light emitting layer 5 (mCP and compound 3 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Example 17

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light-emitting layer 5 (mCP and compound 10 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Example 18

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light emitting layer 5 (mCP and compound 23 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Example 19

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light emitting layer 5 (mCP and compound 30 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Example 20

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light emitting layer 5 (mCP and compound 33 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Example 21

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light emitting layer 5 (mCP and compound 58 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Example 22

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light-emitting layer 5 (mCP and compound 104 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Example 23

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TAPC, thickness 70nm)/light emitting layer 5 (mCP and compound 115 are mixed in a weight ratio of 100:4, thickness 25nm)/electron transport layer 6 (TPBi, thickness 35nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Table 5 shows the test results of the fabricated OLED light-emitting device.

Table 4

table 5

Device code Current efficiency (cd/A) color LT95 service life (Hr) Comparative example 1 1.0 blue 1.0 Example 16 1.2 blue 1.2 Example 17 1.5 blue 1.1 Example 18 1.3 blue 1.2 Example 19 1.1 blue 1.1 Example 20 1.2 blue 1.3 Example 21 1.3 blue 1.4 Example 22 1.2 blue 1.1 Example 23 1.4 blue 1.6

Explanation: the device test performance takes comparative example 1 as a reference, and the various performance indexes of the device of comparative example 1 are set to 1.0. The current efficiency of Comparative Example 1 is 10.8cd/A (@10mA/cm ² ); the CIE color coordinates are (0.14,0.32); the LT95 life decay is 2.2Hr at 1500nit brightness. The life test system is an OLED device life tester jointly researched by the proprietor of the present invention and Shanghai University.

It can be seen from the results in Table 3 that the compound of the present invention can be applied to the manufacture of OLED light-emitting devices, and can obtain good device performance. The luminous efficiency and lifetime of the device are greatly improved. The compound of the invention has a good application effect in OLED light-emitting devices, and has a good industrialization prospect.

Examples 24-30 and Comparative Example 2 illustrate the application effect of the compound synthesized in the present invention as the host material of the light-emitting layer in the device. Compared with Example 15, 24-30 of the present invention and Comparative Example 2 have the same manufacturing process of the device, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also kept consistent. It is to change the thickness of the hole transport layer and the composition of the light emitting layer in the device. The structural compositions of the obtained devices are shown in Table 6. The performance test results of each device are shown in Table 7.

Comparative example 2

ITO anode layer 2/hole injection layer 3 (HAT-CN, thickness 10nm)/hole transport layer 4 (TCPA, thickness 140nm)/light-emitting layer 5 (mCP and RD-1 are mixed in a weight ratio of 100:4, thickness 30nm)/electron transport layer 6 (TPBi, thickness 40nm)/electron injection layer 7 (LiF, thickness 1nm)/cathode reflective electrode layer 8 (Al, thickness 80nm).

Table 6

Table 7

From the results in Table 5, it can be seen that the compound described in the present invention can be used as an auxiliary host material for the light-emitting layer to make OLED light-emitting devices, and compared with Comparative Example 2, both the efficiency and the service life are greatly improved compared with known OLED materials. , especially the driving life of the device has been greatly improved.

While this invention has been disclosed by way of example and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiment. On the contrary, it should be understood by those skilled in the art that various modifications and similar arrangements are intended to be covered. Accordingly, the scope of the appended claims should be accorded the broadest interpretation to cover all such modifications and similar arrangements.

Claims (6)

1. a kind of compound with Quinazol derivative as core, it is characterised in that the compound structure such as formula (1) institute Show：

In formula (1), Ar₁、Ar₂Expression independentlyOr-R；

Wherein, Ar represents C_5-20Aryl；N takes 1 or 2；

R chooses hydrogen or structure shown in formula (2), and Ar₁、Ar₂In R at least one choose structure shown in formula (2)：

In formula (2), R₁、R₂Selection hydrogen independently, C_1-10The alkyl of straight or branched, C_5-20Cycloalkyl, C_5-20Virtue Base, C_5-20Heteroaryl or structure shown in formula (3)；

In formula (3), R₃、R₄Selection C independently_1-10Straight or branched alkyl, C_5-20Cycloalkyl, C_5-20Aryl or C_5-20Heteroaryl.

2. compound according to claim 1, it is characterised in that R1, R2 selection independently are led in the formula (2) Formula (4), formula (5) or structure shown in formula (6)：

Wherein, X is expressed as oxygen atom, sulphur atom, selenium atom, C described in formula (5), formula (6)_1-10Straight or branched alkyl takes One kind in alkylidene, the alkylidene of aryl substitution, the secondary amine of alkyl or aryl substitution in generation.

3. compound according to claim 1, it is characterised in that R is in the formula (1)：

In any one.

4. compound according to claim 1, it is characterised in that the concrete structure formula of the compound is：

In any one.

5. a kind of luminescent device comprising compound described in any one of Claims 1 to 4, it is characterised in that the compound conduct Emitting layer material, for making OLED.

6. a kind of method for preparing compound described in any one of Claims 1 to 4, it is characterised in that generation in preparation process Reaction equation is：

X each independent expression Cl, Br or I in reaction equation 1~2；

N, m independently be expressed as 0 or 1；

The preparation method of wherein reaction equation 1 is：

Weigh halides, the Ar of quinazolinone₁-H、Ar₂- H, is dissolved with toluene；Add Pd₂(dba)₃, tri-butyl phosphine, tertiary fourth Sodium alkoxide；Under an inert atmosphere, by the mixed solution of above-mentioned reactant in 95~110 DEG C of reaction temperature, react 10~24 hours, it is cold But and filtering reacting solution, filtrate revolving, crosses silicagel column, obtains target product；

The halides and Ar of the quinazolinone₁-H、Ar₂The mol ratio of-H is 1:0.8~2.0:0.8~2.0, Pd₂(dba)₃With The mol ratio of the halides of quinazolinone is 0.006~0.02:1, the mol ratio of the halides of tri-butyl phosphine and quinazolinone It is 0.006~0.02:1, sodium tert-butoxide is 1.0~3.0 with the mol ratio of the halides of quinazolinone:1；

The preparation method of reaction equation 2 is：

Weigh halides, the Ar of quinazolinone₁-B(OH)₂、Ar₂-B(OH)₂, it is 2 with volume ratio:1 toluene alcohol mixed solvent Dissolving；Under an inert atmosphere, Na is added₂CO₃The aqueous solution, Pd (PPh₃)₄；By the mixed solution of above-mentioned reactant in reaction temperature 95~110 DEG C of degree, reacts 10~24 hours, cools down and filtering reacting solution, filtrate revolving, crosses silicagel column, obtains target product；

The halogenated compound and Ar of the quinazolinone₁-B(OH)₂、Ar₂-B(OH)₂Mol ratio be 1:1.0~2.0:1.0~ 2.0；Na₂CO₃It is 1.0~3.0 with the mol ratio of the halides of quinazolinone:1；Pd(PPh₃)₄With the halides of quinazolinone Mol ratio is 0.006~0.02:1.