WO2018033085A1 - Compound using anthrone as core and applications thereof in oled component - Google Patents

Abstract

Disclosed are a compound using anthrone as a core and applications thereof in an organic electroluminescent component. The compound uses anthrone as a parent core, which is connected to an aromatic heterocyclic group, so that the molecular symmetry is destroyed, the molecular crystallinity is destroyed, the aggregation effect among the molecules is avoided, and the compound has a good film forming property. The compound serving as a luminescent layer material is used on an organic light-emitting diode, and the OLED component using the compound has good photoelectric performance and can satisfy requirements of a panel manufacturing enterprise.

Description

A compound based on anthrone and its application in OLED devices Technical field

The present invention relates to the field of semiconductor technology, and in particular to an anthrone-based compound and its use as an luminescent layer material on an organic light emitting diode.

Background technique

Organic Light Emitting Diodes (OLED) has become a hot emerging flat panel display product at home and abroad. This is because OLED displays have self-luminous, wide viewing angle (above 175°), short reaction time, high luminous efficiency, and wide color. Domain, low operating voltage (3 ~ 10V), thin panel (less than 1mm) and can be curled. OLED is hailed as a star flat display product in the 21st century. As the technology matures, it is likely to develop rapidly in the future, and the future is boundless.

The principle of OLED luminescence is that after applying an applied voltage, holes and electrons overcome the interface energy barrier, and are injected by the anode and the cathode, respectively entering the HOMO energy level of the hole transport layer and the LUMO energy level of the electron transport layer; and the post charge is added. The electric field is driven to the interface between the hole transport layer and the electron transport layer, and the energy level difference of the interface causes the interface to accumulate charges; the electrons and holes recombine in the organic substance having the luminescent property to form an exciton. This exciter is unstable in the general environment and will then release energy in the form of light or heat back to a stable ground state. The excited state generated by recombination of electrons and holes is theoretically only 25% is a singlet excited state, and the remaining 75% is a triplet excited state, which will return to the ground state in the form of phosphorescence or heat.

The use of organic light-emitting diodes (OLEDs) in large-area flat panel displays and illumination has attracted widespread attention in industry and academia. However, conventional organic fluorescent materials can only emit light with 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). External quantum efficiency is generally less than 5%, which is far from the efficiency of phosphorescent devices. Although the phosphorescent material enhances the intersystem crossing due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device is 100%. However, phosphorescent materials are expensive, the material stability is poor, and the efficiency of the device is seriously reduced, which limits its application in OLEDs. Thermally activated delayed fluorescence (TADF) materials are the third generation of organic luminescent materials developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔE _ST ), and triplet excitons can be converted into singlet exciton luminescence by inter-system enthalpy. 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 material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the field of OLEDs is broad.

Although theoretically TADF materials can achieve 100% exciton utilization, there are actually the following problems: (1) The T1 and S1 states of the design molecule have strong CT characteristics, and very small S1-T1 state energy gaps, although High T ₁ →S ₁ state exciton conversion is achieved by the TADF process, but at the same time results in a low S1 state radiation transition rate, and therefore, it is difficult to achieve (or simultaneously achieve) high exciton utilization and high fluorescence radiation efficiency; Even though doped devices have been used to mitigate the T exciton concentration quenching effect, most TADF material devices have a significant efficiency roll-off at high current densities.

As far as the actual demand of the current OLED display lighting industry is concerned, the development of OLED materials is still far from enough. It is lagging behind the requirements of panel manufacturers, and it is especially important to develop higher performance organic functional materials as material enterprises.

Summary of the invention

In response to the above problems in the prior art, the Applicant provides an anthrone-based compound and its use in OLED devices. The fluorenone compound based on the TADF mechanism is applied to the organic light emitting diode as the light emitting layer material, and the OLED device using the compound of the invention has good photoelectric performance and can meet the requirements of the panel manufacturing enterprise.

The technical solution of the present invention is as follows:

The Applicant provides a compound having an anthrone as a core, the structure of which is as shown in the general formula (1):

Or diphenyl, terphenyl, naphthyl, anthracenyl or phenanthryl; m, n are independently selected 1 or 2;

Said

Indicates that (Ar) _{m is} attached to any carbon atom on the benzene ring on both sides of the formula (1);

R is represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5):

among them,

X ₁ , Y are an oxygen atom, a sulfur atom, a selenium atom, a C _1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl substituted tertiary amine group. a kind

R _{1 is} selected from the structure represented by the general formula (6), and R _{2 is} selected from the structure represented by the general formula (7):

a is

X ₂ and X ₃ are each represented by an oxygen atom, a sulfur atom, a selenium atom, a C _1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl group substituted tertiary group. One of the amine groups; a through the C _L1 -C _L2 bond, the C _L2 -C _L3 bond, the C _L3 -C _L4 bond, the C _L4 -C _L5 bond, the C _L'1 -C _L'2 bond, C _{L a '2} -C _L'3 bond, a C _L'3 -C _L'4 bond or a C _L'4 -C _L'5 bond is attached to the formula (2) or the formula (4);

Ar ₂ and Ar ₃ are each independently represented by a phenyl group, a C _1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, or a naphthyl group;

R ₃ and R ₄ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 50 carbon atoms, an aryl group or an alkyl group substituted with 1 to 1 carbon atom. The 50 amino group, substituted or unsubstituted carbon atom is a heteroaryl group of 1 to 50.

Preferably, the R ₃ and R ₄ are each independently selected from the group consisting of an alkyl group having a carbon atom of 1-10, a phenyl group, a C _1-10 linear or branched alkyl group substituted phenyl group, a diphenyl group, a terphenyl group. a structure represented by a group, a naphthyl group, a formula (8), a formula (9), a formula (10) or a formula (11);

Wherein, Ar ₄ , Ar ₅ and Ar ₆ each independently represent a phenyl group, a C _1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, a naphthyl group, and a C _1-10 straight A chain or branched alkyl substituted benzofuranyl group, a C _1-10 straight or branched alkyl substituted benzothienyl group, a C _1-10 straight or branched alkyl substituted fluorenyl group, C _{1- One of 10} linear or branched alkyl substituted oxazolyl groups;

R ₅ and R ₆ are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 4 to 20 carbon atoms;

X ₄ represents an oxygen atom, a sulfur atom, a selenium atom, a C _1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl substituted tertiary amine group. One.

Preferably, Ar is expressed as

The structural formula of the compound is expressed as:

Any of them.

Preferably, when Ar is represented by R, the structural formula of the compound is expressed as:

Any of them.

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

Any of them.

Preferably, the specific structure of the compound having an fluorenone as a core is:

Any of them.

The Applicant also provides a light-emitting device comprising the compound as a light-emitting layer material for producing an organic electroluminescent device.

Preferably, the compound is used as a host material of the light-emitting layer for producing an organic electroluminescence device.

The Applicant also provides a method of preparing the compound, the reaction equation occurring during the preparation is:

The reaction process of Formula 1 is as follows: the ketone compound and the RH which are the core of the anthrone are weighed and dissolved in toluene; then Pd ₂ (dba) ₃ , tri-tert-butylphosphine and sodium t-butoxide are added; under an inert atmosphere, the above The mixed solution of the reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain a target product;

The molar ratio of bromide to RH of the anthrone is 1:1.0-4.0; the molar ratio of Pd ₂ (dba) ₃ to the bromide of the fluorenone is 0.006-0.02:1, tri-tert-butylphosphine The molar ratio of the bromide with the fluorenone as the core is 0.006 to 0.02:1, and the molar ratio of the sodium bromide to the ketone as the core bromide is 1.0 to 4.0:1;

The reaction process of the formula 2 is as follows: the ketone compound having the anthrone as the core and the Ar-B(OH) ₂ are weighed and dissolved in toluene; then Pd(PPh ₃ ) ₄ and sodium carbonate are added; the above reactant is obtained under an inert atmosphere. The mixed solution is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled, filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain a target product;

The molar ratio of the ketone as the core bromide to Ar-B(OH) ₂ is 1:1.0-4.0; the molar ratio of Pd(PPh ₃ ) ₄ to the ketone as the core bromide is 0.006-0.02:1. The molar ratio of sodium carbonate to ketone as the core bromide is 1.0 to 4.0:1.

The beneficial technical effects of the present invention are:

The compound of the invention uses anthrone as a mother core, destroys the crystallinity of the molecule, avoids the aggregation between molecules, and has good thermal stability; the structural molecule of the compound contains an electron donor (donor, D) and an electron acceptor. The combination of (acceptor, A) can increase the orbital overlap, improve the luminous efficiency, and simultaneously connect the aromatic heterocyclic group to obtain the HOMO, LUMO spatially separated charge transfer state material, and realize the energy level difference between the small S1 state and the T1 state, thereby It is suitable for use as a host material for the light-emitting layer material by realizing the reverse intersystem crossing under thermal stimulation conditions.

The compound of the invention can be used as a host material of the light-emitting layer for the fabrication of the OLED light-emitting device, and obtains good device performance, 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 obviously improved. . The compound material of the invention has good application effect in the OLED light-emitting device and has good industrialization prospect.

DRAWINGS

Figure 1 is a schematic view showing the structure of a device applied to the compound of the present invention;

Wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light-emitting layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode electrode layer. .

detailed description

The present invention will be specifically described below in conjunction with the accompanying drawings and embodiments.

Synthesis of Compound C03 of Example 1

A 250 ml four-necked flask was charged with 0.01 mol of 2-bromo-10,10-dimethyl-10H-fluorenone, 0.015 mol of compound A1, 0.03 mol of sodium t-butoxide, 1×10 ^- under a nitrogen atmosphere. ⁴ mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, the filtrate is steamed, passed through a silica gel column, The target product was 99.40% pure and the yield was 36.90%.

HPLC-MS: The material had a molecular weight of 686.29 and a molecular weight of 686.31.

Synthesis of Compound C11 of Example 2

A 250 ml four-necked flask was charged with 0.01 mol of 3-(3-bromophenyl)-10,10-diphenyl-10H-fluorenone, 0.015 mol of A2, and 0.03 mol of sodium t-butoxide, under a nitrogen atmosphere. 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. A silica gel column gave the desired product with a purity of 97.6% and a yield of 45.8%.

HPLC-MS: The material had a molecular weight of 912.41 and a molecular weight of 912.59.

Synthesis of Compound C24 of Example 3

A 500-ml four-necked flask was charged with 0.01 mol of 3-bromo-10,10-diphenyl-10H-fluorenone, 0.015 mol of A3 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na ₂ CO ₃ (2 M) was added, then 0.0001 mol of Pd(PPh ₃ ) _{4 was added} , and the mixture was heated under reflux for 10 to 24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 99.50% and the yield was 56.5%.

HPLC-MS: The material had a molecular weight of 683.32 and a molecular weight of 683.42.

Synthesis of Compound C31 of Example 4

A 500-ml four-necked flask was charged with 0.01 mol of 3-bromo-10,10-dimethyl-10H-fluorenone, 0.015 mol of A4 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na ₂ CO ₃ (2 M) was added, then 0.0001 mol of Pd(PPh ₃ ) _{4 was added} , and the mixture was heated under reflux for 10 to 24 hours, and the plate was sampled and the reaction was completed. The mixture was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 99.5% and the yield was 38.60%.

HPLC-MS: The material had a molecular weight of 712.35 and a molecular weight of 712.4.

Synthesis of Compound C36 of Example 5

A 250 ml four-necked flask was charged with 0.01 mol of 3-(4-bromophenyl)-10,10-dimethyl-10H-fluorenone, 0.015 mol of A5, 0.03 mol of sodium t-butoxide, under a nitrogen atmosphere. 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. A silica gel column gave the desired product with a purity of 97.2% and a yield of 45.6%.

HPLC-MS: The material had a molecular weight of 781.33 and a molecular weight of 781.28.

Synthesis of Compound C48 of Example 6

A 500-ml four-necked flask was charged with 0.01 mol of 2-bromo-10,10-diphenyl-10H-fluorenone, 0.015 mol of A3 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na ₂ CO ₃ (2 M) was added, then 0.0001 mol of Pd(PPh ₃ ) _{4 was added} , and the mixture was heated under reflux for 10 to 24 hours, and the plate was sampled and the reaction was completed. The mixture was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 99.2% and the yield was 56.3%.

HPLC-MS: The material had a molecular weight of 887.39 and a molecular weight of 887.42.

Synthesis of Compound C50 of Example 7

A 250 ml four-necked flask was charged with 0.01 mol of 3-(4-bromophenyl)-10,10-dimethyl-10H-fluorenone, 0.015 mol of A7, 0.03 mol of sodium t-butoxide, under a nitrogen atmosphere. 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. A silica gel column gave the desired product with a purity of 97.1% and a yield of 45.8%.

HPLC-MS: The material had a molecular weight of 963.42 and a molecular weight of 963.38.

Synthesis of Compound C60 of Example 8

A 250 ml four-necked flask was charged with 0.01 mol of 3-bromo-10,10-dimethyl-10H-fluorenone, 0.015 mol of A8, 0.03 mol of sodium t-butoxide, and 1 x 10 ^-4 mol under a nitrogen atmosphere. Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed and passed through a silica gel column to obtain the desired product. The purity was 96.8%, and the yield was 45.4%.

HPLC-MS: The molecular weight of the material was 768.41, and the measured molecular weight was 768.35.

Synthesis of Compound C64 of Example 9

A 250 ml four-necked flask was charged with 0.01 mol of 3-(4-bromophenyl)-10,10-dimethyl-10H-fluorenone, 0.015 mol of A9, and 0.03 mol of sodium tert-butoxide under a nitrogen atmosphere. 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. A silica gel column gave the desired product with a purity of 97.5% and a yield of 45.6%.

HPLC-MS: The material had a molecular weight of 872.38 and a molecular weight of 872.42.

Synthesis of Compound C71 of Example 10

A 250 ml four-necked flask was charged with 0.01 mol of 3-(4-bromophenyl)-10,10-dimethyl-10H-fluorenone, 0.015 mol of A10, 0.03 mol of sodium t-butoxide, under a nitrogen atmosphere. 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. A silica gel column gave the desired product, purity 97.1%, yield 46.6%.

HPLC-MS: The material had a molecular weight of 835.36 and a molecular weight of 835.42.

Synthesis of Compound C79 of Example 11

A 250 ml four-necked flask was charged with 0.01 mol of 3-(3-bromophenyl)-10,10-diphenyl-10H-fluorenone, 0.015 mol of A11, 0.03 mol of sodium t-butoxide, under a nitrogen atmosphere. 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. A silica gel column gave the desired product with a purity of 97.2% and a yield of 44.3%.

HPLC-MS: The material had a molecular weight of 844.31 and a molecular weight of 844.36.

Synthesis of Compound C109 of Example 12

A 500-ml four-necked flask was charged with 0.01 mol of 3-bromo-10,10-diphenyl-10H-fluorenone, 0.015 mol of A12 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na ₂ CO ₃ (2 M) was added, then 0.0001 mol of Pd(PPh ₃ ) _{4 was added} , and the mixture was heated under reflux for 10 to 24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 96.50% and the yield was 53.5%.

HPLC-MS: The material had a molecular weight of 768.28 and a molecular weight of 768.34.

Synthesis of Compound C121 of Example 13

A 500-ml four-necked flask was charged with 0.01 mol of 3-bromo-10,10-dimethyl-10H-fluorenone, 0.015 mol of A13 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na ₂ CO ₃ (2 M) was added, then 0.0001 mol of Pd(PPh ₃ ) _{4 was added} , and the mixture was heated under reflux for 10 to 24 hours, and the plate was sampled and the reaction was completed. The mixture was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to give the desired product. The HPLC purity was 94.50% and the yield was 52.5%.

HPLC-MS: The material had a molecular weight of 871.38 and a molecular weight of 871.42.

Synthesis of Compound C123 of Example 14

A 500-ml four-necked flask was charged with 0.01 mol of 2-bromo-10,10-dimethyl-10H-fluorenone, 0.015 mol of A14 under a nitrogen atmosphere, dissolved in a mixed solvent (180 ml of toluene, 90 ml of ethanol), and then 0.03 mol of an aqueous solution of Na ₂ CO ₃ (2 M) was added, then 0.0001 mol of Pd(PPh ₃ ) _{4 was added} , and the mixture was heated under reflux for 10 to 24 hours, and the plate was sampled and the reaction was completed. It was naturally cooled, filtered, and the filtrate was evaporated to dryness to silica gel column to afford the desired product. The HPLC purity was 91.50% and the yield was 53.5%.

HPLC-MS: The material had a molecular weight of 645.23 and a molecular weight of 645.35.

Synthesis of Compound C132 of Example 15

A 500-ml four-necked flask was charged with 0.01 mol of 2-(3,5-dibromophenyl)-10,10-dimethyl-10H-fluorenone, 0.015 mol of A15 under a nitrogen atmosphere, dissolved in a mixed solvent. (180ml of toluene, 90ml ethanol), followed by addition of 0.03molNa ₂ CO ₃ aq (2M) was added 0.0001mol Pd (PPh _{3) 4,} was heated at reflux for 10-24 hours, and sampling, the reaction was complete. It was naturally cooled, filtered, and the filtrate was evaporated to dryness. The title compound was obtained from the silica gel column. The HPLC purity was 97.10% and the yield was 30.60%.

HPLC-MS: The material had a molecular weight of 814.27 and a molecular weight of 814.32.

Synthesis of Compound 16 of Example 16 C133

A 250 ml four-necked flask was charged with 0.01 mol of 3,6-(4-bromophenyl)-10,10-dimethyl-10H-fluorenone, 0.03 mol of A16, 0.03 mol of tert-butanol under a nitrogen atmosphere. Sodium, 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heated under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. After passing through a silica gel column, the target product was obtained, the purity was 98.61%, and the yield was 49.50%.

HPLC-MS: The material had a molecular weight of 1122.52 and a molecular weight of 1122.48.

Synthesis of Example 17 Compound C136

A 250 ml four-necked flask was charged with 0.01 mol of 2-(4-bromophenyl)-10,10-diphenyl-10H-fluorenone, 0.03 mol of A17, 0.03 mol of sodium t-butoxide, under a nitrogen atmosphere. 1 × 10 ^-4 mol Pd ₂ (dba) ₃ , 1 × 10 ^-4 mol of tri-tert-butylphosphine, 150 ml of toluene, heating under reflux for 24 hours, sampling the plate, the reaction is complete, naturally cooled, filtered, and the filtrate is steamed. The silica gel column gave the target product with a purity of 98.61% and a yield of 49.50%.

HPLC-MS: The material had a molecular weight of 753.30 and a molecular weight of 753.34.

The compound of the present invention can be used as a light-emitting layer material, and the thermal properties and HOMO levels of the compound C36 of the present invention and the conventional material CBP are respectively measured, and the test results are shown in Table 1.

Table 1

Compound	Tg (°C)	Td (°C)	HOMO level (eV)	function
Compound C36	153	412	-5.70	Body material
Compound CBP	113	353	-5.90	Body material

Note: The glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Germany), the heating rate is 10 ° C / min; the weight loss temperature Td is the temperature loss of 1% in the nitrogen atmosphere, The measurement was carried out on a TGA-50H thermogravimetric analyzer of Shimadzu Corporation, Japan, with a nitrogen flow rate of 20 mL/min; the highest occupied molecular orbital HOMO level and the lowest occupied molecular orbital LUMO level were determined by a photoelectron emission spectrometer (AC-2 type). Calculated by PESA) and UV spectrophotometer (UV) test, the test is atmospheric.

As can be seen from the above table data, the compound of the present invention has high thermal stability and an appropriate HOMO level. Suitable as a light-emitting layer material; at the same time, the compound of the present invention contains an electron donor (donor, D) and an electron acceptor (acceptor, A), so that the electrons and holes of the OLED device to which the compound of the present invention is applied are balanced, so that the device efficiency and Life is improved.

The application effects of the compound synthesized by the present invention as a host material of the light-emitting layer in the device will be described in detail below by Examples 18-25 and Comparative Examples 1-3. Embodiments 19-25 Compared with Example 18, the fabrication process of the device is identical, and the same substrate material and electrode material are used, and the film thickness of the electrode material is also uniform, except that the light-emitting layer in the device is different. The subject material has changed. Examples 18-25 Compared with Comparative Examples 1-3, the light-emitting layer materials of the devices of Comparative Examples 1-3 were conventional materials, and the light-emitting layer host materials of Examples 18-25 were Inventive compound. The structural composition of the device obtained in each example is shown in Table 2. The performance test results of each device are shown in Table 3.

Example 18

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C24 and GD-19 according to 100 : 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al). The molecular structure of each compound is as follows:

The specific preparation process is as follows:

The transparent substrate layer 1 is made of a transparent material such as glass; the ITO anode layer 2 (having a film thickness of 150 nm) is washed, that is, sequentially washed with alkali, washed with pure water, dried, and then subjected to ultraviolet-ozone washing to remove the organic surface of the transparent ITO. the remains.

On the ITO anode layer 2 after the above washing, molybdenum trioxide MoO ₃ having a thickness of 10 nm was deposited as a hole injecting layer 3 by a vacuum vapor deposition apparatus. Next, a TASC having a thickness of 80 nm was evaporated as the hole transport layer 4.

After the vapor deposition of the hole transporting material is completed, the light emitting layer 5 of the OLED light emitting device is formed, and the structure thereof comprises the material compound C02 used as the host material of the OLED light emitting layer 5, and GD-19 is used as a doping material, and the doping ratio of the doping material is The film thickness of the light-emitting layer was 5% by weight.

After the above-mentioned light-emitting layer 5, the vacuum evaporation electron-transporting layer material was continued to be TPBI, and the vacuum-deposited film thickness of the material was 40 nm, and this layer was the electron-transport layer 6.

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

On the electron injecting layer 7, an aluminum (Al) layer having a film thickness of 80 nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflective electrode layer 8.

After the OLED light-emitting device is completed as described above, the anode and the cathode are connected by a known driving circuit, and the luminous efficiency, the luminescence spectrum, and the current-voltage characteristics of the device are measured.

Example 19

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C36 and GD-19 according to 100 : 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Example 20

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compound C24 and Ir (PPy) 3 The mixture was mixed in a weight ratio of 100:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Example 21

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C31 and Ir (PPy) 3 The mixture was mixed in a weight ratio of 100:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Example 22

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compound 36 and GD-PACTZ according to 100 : 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Example 23

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compound C71 and GD-PACTZ according to 100 : 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Example 24

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C123, GH-204 and Ir (PPy) 3 was blended in a weight ratio of 70:30:10, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Example 25

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (compounds C136, GH-204 and GD - PACTZ was blended in a weight ratio of 70:30:5, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Comparative example 1

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (CBP and GD-19 according to 100: 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Comparative example 2

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (CBP and Ir (PPy) 3 according to 100:10 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

Comparative example 3

Transparent substrate layer 1 / ITO anode layer 2 / hole injection layer 3 (molybdenum trioxide MoO ₃ , thickness 10 nm) / hole transport layer 4 (TAPC, thickness 80 nm) / luminescent layer 5 (CBP and GD-PACTZ according to 100: 5 by weight blending, thickness 30 nm) / electron transport layer 6 (TPBI, thickness 40 nm) / electron injection layer 7 (LiF, thickness 1 nm) / cathode electrode layer 8 (Al).

The test results of the fabricated OLED light-emitting device are shown in Table 3.

Table 2

table 3

It can be seen from the results of Table 3 that the compound of the present invention can be used as a host material of the light-emitting layer to be fabricated with an OLED light-emitting device, and compared with Comparative Example 1-3, both the efficiency and the lifetime are larger than those of the known OLED material. The improvement, especially the drive life of the device, has been greatly improved.

From the above data application, the compound of the invention has good application effect as an luminescent layer material in an OLED light-emitting device, and has a good industrialization prospect.

While the invention has been disclosed by the embodiments and the preferred embodiments, it is understood that the invention is not limited to the disclosed embodiments. Instead, it will be apparent to those skilled in the art that the various modifications and similar arrangements are contemplated. Therefore, the scope of the appended claims should be accorded

Claims (9)

1. A compound having an anthrone as a core, characterized in that the structure of the compound is as shown in the formula (1):

   

   

   Or diphenyl, terphenyl, naphthyl, anthracenyl or phenanthryl; m, n are independently selected 1 or 2;

   Said Indicates that (Ar) _{m is} attached to any carbon atom on the benzene ring on both sides of the formula (1);

   R is represented by the general formula (2), the general formula (3), the general formula (4) or the general formula (5):

   

   among them,

   X ₁ , Y are an oxygen atom, a sulfur atom, a selenium atom, a C _1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl substituted tertiary amine group. a kind

   R _{1 is} selected from the structure represented by the general formula (6), and R _{2 is} selected from the structure represented by the general formula (7):

   

   a is

   

   X ₂ and X ₃ are each represented by an oxygen atom, a sulfur atom, a selenium atom, a C _1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl group substituted tertiary group. One of the amine groups; a through the C _L1 -C _L2 bond, the C _L2 -C _L3 bond, the C _L3 -C _L4 bond, the C _L4 -C _L5 bond, the C _L'1 -C _L'2 bond, C _{L a '2} -C _L'3 bond, a C _L'3 -C _L'4 bond or a C _L'4 -C _L'5 bond is attached to the formula (2) or the formula (4);

   Ar ₂ and Ar ₃ are each independently represented by a phenyl group, a C _1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, or a naphthyl group;

   R ₃ and R ₄ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 50 carbon atoms, an aryl group or an alkyl group substituted with 1 to 1 carbon atom. The 50 amino group, substituted or unsubstituted carbon atom is a heteroaryl group of 1 to 50.
2. The compound according to claim 1, wherein said R ₃ and R ₄ are each independently selected from the group consisting of an alkyl group having a carbon atom of 1 to 10, a phenyl group, a C _1-10 linear or branched alkyl group substituted benzene. a structure represented by a group, a diphenyl group, a terphenyl group, a naphthyl group, a formula (8), a formula (9), a formula (10) or a formula (11);

   

   Wherein, Ar ₄ , Ar ₅ and Ar ₆ each independently represent a phenyl group, a C _1-10 linear or branched alkyl substituted phenyl group, a diphenyl group, a terphenyl group, a naphthyl group, and a C _1-10 straight A chain or branched alkyl substituted benzofuranyl group, a C _1-10 straight or branched alkyl substituted benzothienyl group, a C _1-10 straight or branched alkyl substituted fluorenyl group, C _{1- One of 10} linear or branched alkyl substituted oxazolyl groups;

   R ₅ and R ₆ are each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 4 to 20 carbon atoms;

   X ₄ represents an oxygen atom, a sulfur atom, a selenium atom, a C _1-10 linear or branched alkyl substituted alkylene group, an aryl substituted alkylene group, an alkyl group or an aryl substituted tertiary amine group. One.
3. The compound according to claim 1, wherein Ar is represented by

   

   The structural formula of the compound is expressed as:

   

   

   Any of them.
4. The compound according to claim 1, wherein when Ar is represented by -R, the structural formula of the compound is expressed as:

   

   Any of them.
5. The compound according to claim 1, wherein R in the formula (1) is:

   

   

   

   

   

   

   or

   

   Any of them.
6. The compound according to claim 1, characterized in that the specific structure of the compound having an fluorenone as a core is:

   

   

   

   

   

   

   

   

   

   

   Any of them.
7. A light-emitting device comprising the compound according to any one of claims 1 to 6, characterized in that the compound is used as a light-emitting layer material for producing an organic electroluminescence device.
8. The light emitting device according to claim 7, wherein said compound is used as a host material of a light-emitting layer for producing an organic electroluminescence device.
9. A process for the preparation of a compound according to any one of claims 1 to 6, characterized in that the reaction equation which occurs during the preparation is:

   

   

   The reaction process of Formula 1 is as follows: the ketone compound and the RH which are the core of the anthrone are weighed and dissolved in toluene; then Pd ₂ (dba) ₃ , tri-tert-butylphosphine and sodium t-butoxide are added; under an inert atmosphere, the above The mixed solution of the reactants is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled and filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain a target product;

   The molar ratio of bromide to RH of the anthrone is 1:1.0-4.0; the molar ratio of Pd ₂ (dba) ₃ to the bromide of the fluorenone is 0.006-0.02:1, tri-tert-butylphosphine The molar ratio of the bromide with the fluorenone as the core is 0.006 to 0.02:1, and the molar ratio of the sodium bromide to the ketone as the core bromide is 1.0 to 4.0:1;

   The reaction process of the formula 2 is as follows: the ketone compound having the anthrone as the core and the Ar-B(OH) ₂ are weighed and dissolved in toluene; then Pd(PPh ₃ ) ₄ and sodium carbonate are added; the above reactant is obtained under an inert atmosphere. The mixed solution is reacted at a reaction temperature of 95 to 110 ° C for 10 to 24 hours, and the reaction solution is cooled, filtered, and the filtrate is rotary-screwed and passed through a silica gel column to obtain a target product;

   The molar ratio of the ketone as the core bromide to Ar-B(OH) ₂ is 1:1.0-4.0; the molar ratio of Pd(PPh ₃ ) ₄ to the ketone as the core bromide is 0.006-0.02:1. The molar ratio of sodium carbonate to ketone as the core bromide is 1.0 to 4.0:1.

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