WO2020015675A1 - Compound having triarylamine as core and application thereof - Google Patents

Abstract

The present invention belongs to the technical field of semiconductors. Disclosed are a compound having triarylamine as a core and an application thereof. The structure of the compound provided in the present invention is represented by general formula (I). Also disclosed are a preparation method for and an application of said compound. The compound of the present invention has high glass transition temperature and molecular thermal stability, suitable HOMO and LUMO energy levels, and high mobility. By optimizing the structure of devices, the photoelectric performance and lifetime of OLED devices can be largely improved.

Description

Compound with triarylamine as core and application thereof Technical field

The invention relates to a compound having a triarylamine as a core, a preparation method and an application thereof, and belongs to the field of semiconductor technology.

Background technique

Organic electroluminescence (OLED: Organic Light Emission Diodes) device technology can be used to manufacture both new display products and new lighting products. It is expected to replace the existing liquid crystal display and fluorescent lamp lighting and has a wide application prospect.

At present, OLED display technology has been applied in smart phones, tablet computers and other fields, and it will further expand to large-scale applications such as televisions. However, compared with the actual product application requirements, the OLED device's luminous efficiency and service life and other performance Need to be further improved.

Studies on improving the performance of OLED light-emitting devices include: reducing the driving voltage of the device, improving the light-emitting efficiency of the device, and increasing the service life of the device. In order to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and manufacturing process of OLED devices, but also to continuously research and innovate OLED optoelectronic functional materials to create higher-performance OLED functional materials.

The OLED photoelectric functional material film layer constituting the OLED device includes at least two layers. The OLED device structure applied in industry includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. And other film layers, that is to say, the optoelectronic functional materials used in OLED devices include at least hole injection materials, hole transport materials, luminescent materials, and electron transport materials. The types and combinations of materials are rich and diverse. . In addition, for the matching of OLED devices with different structures, the optoelectronic functional materials used have strong selectivity, and the performance of the same materials in devices with different structures may also be completely different.

Therefore, according to the current industrial application requirements of OLED devices, as well as the different functional film layers of OLED devices, and the optical and electrical characteristics of the devices, it is necessary to choose more suitable and high-performance OLED functional materials or material combinations to achieve high efficiency and long life of the devices. And low voltage. As far as the actual needs of the current OLED display and lighting industry are concerned, the development of OLED materials is far from enough, falling behind the requirements of panel manufacturing companies, and it is particularly important for materials companies to develop higher-performance organic functional materials.

Summary of the invention:

In view of the foregoing problems in the prior art, the applicant of the present invention provides a compound having a triarylamine structure as a core and its application to an organic electroluminescent device. The compound of the present invention is not easy to crystallize, has high heat resistance stability, and has high hole mobility, so that the life and efficiency of the device are significantly improved.

A compound with a triarylamine as the core, the structure of the compound is shown by the general formula (1):

The mn can be independently taken as 0 or 1, and mn is not 0 at the same time;

When A is represented by the structure represented by the general formula (2), R is not represented by the structure represented by the general formula (7);

Said a is represented by the number 0, 1, 2, 3 or 4;

The A is a structure represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), or the general formula (6);

In the general formula (3), each of X ₁ X _{2 is} independently represented as -O--S--C (R ₆ ) (R ₇ )-or -N (R ₈ )-;

The general formula (2) may be linked in parallel with the general formula (1) through a C _L1 -C _L2 bond, C _L2 -C _L3 bond or a C _L3 -C _L4 bond; the general formula (3) may be connected through a C _L5- C _L6 bond C _L6 -C _L7 bond or C _L7 -C _L8 bond is connected in parallel with the general formula (1); the general formula (4) can be connected in parallel with the general formula (1) through C _L9 -C _L10 bond ; The general formula (5) may be connected in parallel with the general formula (1) through a C _L11 -C _L12 bond; the general formula (6) may be connected through a C _L13 -C _L14 bond C _L14 -C _L15 bond or C _L15 -C _L16 bond is ring-connected with general formula (1);

The Ar _{1 and} Ar ₂ are each independently represented as a single bond substituted or unsubstituted phenylene substituted or unsubstituted naphthylene substituted or unsubstituted biphenylene substituted or unsubstituted pyridylene;

The R ₁ R ₂ are each independently represented by a structure represented by the general formula (7):

Wherein R ₃ and R ₄ are each independently represented as -KR ₅ ; K is represented by a single bond substituted or unsubstituted phenylene substituted or unsubstituted naphthylene substituted or unsubstituted biphenylene substituted or unsubstituted Pyridinyl; R ₅ is substituted or unsubstituted pyridyl substituted or unsubstituted pyrimidinyl substituted or unsubstituted phenyl substituted or unsubstituted quinolinyl substituted or unsubstituted isoquinolinyl substituted or unsubstituted A diazaphenanthryl substituted or unsubstituted naphthyl substituted or unsubstituted biphenyl structure represented by the general formula (8) or the general formula (9);

The X ₃ X ₄ X ₅ are each independently expressed as a single bond -O--S--C (R ₉ ) (R ₁₀ )-or -N (R ₁₁ )-; and X ₃ X _{4 is} not simultaneously expressed as single bond;

The Z is represented by nitrogen or CR ₁₂ ; and the group K bonded by the group Z represents a carbon atom;

The R represents a hydrogen atom cyano halogen C ₁ -C ₁₀ linear alkyl C ₃ -C ₁₀ branched alkyl substituted or unselected C _6-30 aryl substituted or unsubstituted containing one or more Heteroatom 5- to 30-membered heteroaryl or one of the general formula (7); R may replace any substitutable site in the structure of the general formula (1);

The R ₆ to R ₁₁ each independently represent a C _1-10 alkyl substituted or unsubstituted C _6-30 aryl group containing one or more heteroatom substituted or unsubstituted 5-30 membered heteroaryl groups. R ₆ and R ₇ R ₉ and R ₁₀ may be connected to form a 5- to 30-membered alicyclic or aromatic ring;

The R ₁₂ represents a hydrogen atom halogen cyano C _1-10 alkyl C _1-10 alkenyl substituted or unsubstituted C _6-30 aryl group containing one or more heteroatom substituted or unsubstituted 5 ～ One of 30-membered heteroaryl groups; two or more adjacent R ₁₂ may be connected to form a 5- to 30-membered alicyclic or aromatic ring;

The substituted C _6-30 aryl substituted 5- to 30-membered heteroaryl group containing one or more heteroatoms may optionally contain a halogen cyano C _1-20 alkyl C _6-20 aryl group. One or more of 5-30 membered heteroaryl groups of one or more heteroatoms;

The substituent that replaces the above-mentioned substitutable group may be optionally selected from one or more of a halogen cyano C _1-20 alkyl C _6-20 aryl 5-30 membered heteroaryl group containing one or more heteroatoms ;

The hetero atom is selected from an oxygen atom, a sulfur atom, or a nitrogen atom.

Further, each of the RR _{12 is} independently represented by a hydrogen atom, a fluorine atom, cyanomethylethylpropylisopropylbutylt-butylpentylphenylbiphenyl, terphenylnaphthylpyridyl or furyl;

The R ₆ to R ₁₁ are each independently represented as methylethylpropylisopropylbutylt-butylpentyl substituted or unsubstituted phenyl substituted or unsubstituted biphenyl substituted or unsubstituted naphthyl Substituted or unsubstituted pyridyl;

The substituted C _6-30 aryl substituted 5- to 30-membered heteroaryl group containing one or more heteroatoms may optionally have a fluorine atom cyanomethylethylpropylisopropylbutyl tert-butyl One or more of pentylphenylbiphenylnaphthylpyridyl or furyl.

Further, the general formula (3) can be expressed as the following structure:

Further, in the general formula (7), the R3R4 may be represented by the following structure:

Further, the general formula (1) can be expressed as the following specific structure:

One of them.

The preparation method of the compound, the reaction process during the preparation process is as follows:

When Ar ₁ and Ar ₂ are single bonds, the preparation reaction equation is:

Reactant II amine compound selected from R ₁ -HR ₂ -H

The specific preparation process includes the following steps:

Step 1: Using reactant I and reactant II as raw materials and toluene as a solvent to obtain a reaction system, wherein the amount of toluene used is 30-50 ml per gram of reactant I, and the moles of reactant I and reactant II are The ratio is 1: (1.0-2.0);

Step 2: Add Pd ₂ (dba) ₃ P (t-Bu) ₃ and sodium tert-butoxide to the reaction system of step 1, wherein the molar ratio of Pd ₂ (dba) ₃ to reactant I is (0.005). ～ 0.01): 1, the molar ratio of P (t-Bu) ₃ to reactant I is (1.5 ～ 6.0): 1; the molar ratio of the sodium tert-butoxide to reactant I is (2.0 ～ 5.0) :1;

Step 3: Under the protection of nitrogen, the reaction system of step 2 is reacted at 95 to 110 ° C for 10 to 24 hours, naturally cooled to room temperature, and the reaction solution is filtered. The filtrate is subjected to reduced pressure rotary evaporation and passed through a neutral silica gel column to obtain Target compound

When Ar ₁ and Ar _{2 are} not represented as single bonds, the preparation equation is:

Reactant III boric acid compound selected from

The specific preparation process includes the following steps:

Step 1: Using reactant I and reactant III as raw materials and ethanol and toluene as solvents to obtain a reaction system, wherein the ratio of toluene to ethanol is 2: (0.8-1.2), and the amount of toluene is per gram of reactant I Using 30-50 ml, the molar ratio of reactant I to reactant III is 1: (1.0-3.0);

Step 2: Add Pd (PPh ₃ ) ₄ and sodium carbonate to the reaction system of Step 1; wherein the molar ratio of Pd (PPh ₃ ) ₄ to reactant I is (0.005 ～ 0.02): 1, and the carbonic acid is The molar ratio of sodium to reactant I is (2.0-5.0): 1, and sodium carbonate and water are arranged to obtain a 2-2.5mol / L aqueous solution;

Step 3: Under the protection of nitrogen, the reaction system of step 2 is reacted at 95 to 110 ° C for 10 to 24 hours, naturally cooled to room temperature, and the reaction solution is filtered. The filtrate is subjected to reduced pressure rotary evaporation and passed through a neutral silica gel column to obtain Target compound.

An organic electroluminescent device, at least one functional layer containing the compound.

As a further improvement of the present invention, the functional layer is a hole transporting layer or an electron blocking layer.

A lighting or display element includes the organic electroluminescence device.

The beneficial technical effects of the present invention are:

The p-π conjugate effect in the compound of the present invention makes it have a strong hole transporting ability, and a high hole transporting rate can improve the efficiency of an organic electroluminescent device; the asymmetric triarylamine structure in the compound can reduce the molecular Crystallinity reduces the planarity of the molecule and prevents the molecule from moving on the plane, thereby improving the thermal stability of the molecule. The compound of the present invention uses anthracene helical aryl fluorene as the mother core and connects triarylamine branches, so that the structure has a higher dielectric constant and the compound has a higher refractive index.

The structure of the compound of the present invention makes the distribution of electrons and holes in the light-emitting layer more balanced. Under the proper HOMO energy level, the hole injection and transport performance is improved; at the appropriate LUMO energy level, it also plays an electronic blocking function. Function to improve the recombination efficiency of the exciton in the light-emitting layer; when used as the material of the light-emitting functional layer of the OLED light-emitting device, the anthracene helical aryl group and the branched chain within the scope of the present invention can effectively improve exciton utilization and high fluorescent radiation Efficiency, reducing efficiency roll-off at high current density, reducing device voltage, increasing device current efficiency and life.

When the compound of the present invention is applied to an OLED device, through optimization of the device structure, high film layer stability can be maintained, and the photoelectric performance of the OLED device and the life of the OLED device can be effectively improved. The compound of the invention has good application effect and industrial prospect in OLED light-emitting devices.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic structural diagram of the materials listed in the present invention applied to OLED devices, where the components represented by each reference number are as follows:

1 transparent substrate layer, 2ITO anode layer, 3 hole injection layer, 4 hole transport, 5 electron blocking layer, 6 light emitting layer, 7 hole blocking / electron transport layer, 8 electron injection layer, 9 cathode reflective electrode layer;

FIG. 2 is a graph of efficiency curves of device example 1 device example 4 device example 13 and device comparative example 1 at different temperatures according to the invention.

detailed description

The principles and features of the present invention are described below with reference to the accompanying drawings. The following are only preferred embodiments of the present invention. Any modifications made within the spirit and principle of the present invention, such as equivalent replacements, shall be included in Within the scope of the present invention.

Example 1: Synthesis of reactant I

Step 1: Raw material I and intermediate I are used as raw materials, ethanol and toluene are used as solvents, wherein the ratio of toluene to ethanol is 2: (0.8-1.2), and the amount of toluene used is 30-50 ml per gram of raw material I. Therefore, The molar ratio of the raw material I to the intermediate I is 1: (1.0-1.5); Pd (PPh ₃ ) ₄ and potassium carbonate are added to the reaction solution to prepare a reaction system; wherein the Pd (PPh ₃ ) ₄ and The molar ratio of the raw material I is (0.005 to 0.01): 1, and the potassium carbonate and water are arranged to obtain an aqueous solution of 2-2.5 mol / L; under the protection of nitrogen, the reaction system is reacted at 95 to 110 ° C for 10 to 24 hours, It was naturally cooled to room temperature, and the reaction solution was filtered. The filtrate was subjected to rotary evaporation under reduced pressure and passed through a neutral silica gel column to obtain intermediate II.

Step 2: Dissolve intermediate II with 50-80 mL of dry THF, and keep it at -78 ° C for 30 minutes, then add a 1.2M-1.5M n-butyllithium solution under a nitrogen atmosphere, the intermediate II and n-butyl The molar ratio of lithium base is 1: (0.8-1.1). After stirring for 1 to 2 hours, the raw material II is continuously added under a nitrogen atmosphere. The molar ratio of the intermediate II to the raw material is 1: (0.8-1.2). Stir After homogenization, slowly rise to room temperature. After stirring at room temperature for 10 to 24 hours, add 20-30 mL of water to the reaction system and continue stirring for 1-2 hours. The product precipitates from the reaction system and is filtered to obtain intermediate III.

Step 3: Dissolve intermediate III in a mixed solution of acetic acid and hydrochloric acid, where the volume ratio of acetic acid and hydrochloric acid is 100: (8-10), heat to 110 ° C with stirring, react for 10 hours, and naturally cool to room temperature. The product precipitates. Filtered to wash with water and methanol to obtain reactant I;

Take reactant I-1 as an example:

Step 1: Under a nitrogen atmosphere, said feed taking 0.02mol and 0.02mol Intermediate I-1 I-1 was dissolved in 60ml of toluene: ethanol 2: 1 mixed solvent was added to the reaction solution 0.0002molPd (PPh _{3) 4} And a 0.04 mol potassium carbonate aqueous solution to prepare a reaction system at 110 ° C. for 10 to 24 hours, naturally cooling to room temperature, and filtering the reaction solution. The filtrate was subjected to rotary distillation under reduced pressure and passed through a neutral silica gel column to obtain intermediate II-1. , HPLC purity 95.91%, yield 95.2%.

Step 2: Dissolve 0.02 mol of Intermediate II-1 with 60 mL of dry THF, incubate at -78 ° C for 30 minutes, add 24 mL of 1.2M n-butyllithium solution under a nitrogen atmosphere, and stir for 1 to 2 hours. Continue to add 0.02mol of raw material II-1 under a nitrogen atmosphere, slowly stir to room temperature after stirring well, continue to stir the reaction at room temperature for 10-24 hours, add 20mL of water to the reaction system, and continue stirring for 1-2 hours. Precipitation in the reaction system, filtration, to obtain intermediate III-1, HPLC purity 92.55%, yield 85.7%;

Step 3: Dissolve 0.02mol of intermediate III-1 in a mixed solution of 50mL of acetic acid and 5mL of hydrochloric acid, stir and heat to 110 ° C, react for 10h, naturally cool to room temperature, precipitate the product, and wash it with water and methanol to obtain reactant I- 1. HPLC purity was 99.29%, yield was 75.5%; HRMS (EI) (high resolution mass spectrometry): The theoretical value was 494.0670, and the measured value was 494.0628.

Example 2: Synthesis of Intermediate I

In a nitrogen atmosphere, weigh raw material III bis (pinacol) diboron Pd (dppf) Cl ₂ potassium acetate and dissolve it in toluene, and react at 100 ～ 120 ℃ for 12 ～ 24 hours. Cool naturally, filter, and spin the filtrate to obtain a crude product. Pass the neutral silica gel column to obtain intermediate I. The molar ratio of raw material III to bis (pinacol) diboron is 2: (1 to 1.5). The molar ratio of Pd (dppf) Cl ₂ is 1: (0.01 to 0.05), and the molar ratio of raw material III to potassium acetate is 1: (2 to 2.5);

Take intermediate I-1 as an example:

In a nitrogen atmosphere, weigh 0.02mol of raw material III-10.012mol of bis (pinacol) diboron 0.0002mol Pd (dppf) Cl ₂ 0.05mol potassium acetate dissolved in toluene, and react at 100 ～ 120 ℃ for 12 ～ 24 Hours, the sample was spotted, the reaction was complete, natural cooling, filtration, and the filtrate was spin-evaporated to obtain the crude product, which was passed through a neutral silica gel column to obtain intermediate I-1; HPLC purity 99.35%, yield 76.3%; HRMS (EI): theory The value is 172.0696, and the measured value is 172.0629.

Example 3: Synthesis of Reactant III

Weigh intermediate reactant II and raw material IV and dissolve in toluene; then add Pd ₂ (dba) ₃ P (Ph) ₃ sodium tert-butoxide; under an inert atmosphere, mix the mixed solution of the above reactants at 95 to 110 ° C. The reaction was allowed to proceed for 10 to 24 hours. The reaction solution was cooled and filtered. The filtrate was spin-evaporated and passed through a silica gel column to obtain intermediate IV. The molar ratio of the reactant II to the raw material IV was 1: (1.0 to 1.5). Pd ₂ (dba The molar ratio of ₃ to reactant II is (0.006 to 0.02): 1, and the molar ratio of P (Ph) ₃ to reactant II is (0.006 to 0.02): 1. The molar ratio of sodium tert-butoxide to reactant II It is (1.0 ～ 3.0): 1;

Under a nitrogen atmosphere, the intermediate IV bis (pinacol) diboron Pd (dppf) Cl ₂ potassium acetate was weighed and dissolved in toluene. The reaction was performed at 100 ～ 120 ℃ for 12 ～ 24 hours. The sample was spotted and the reaction was complete. , Natural cooling, filtration, and rotary evaporation of the filtrate to obtain a crude product, passing through a neutral silica gel column to obtain a reactant III; the molar ratio of the intermediate IV to the bis (pinacol) diboron is 2: (1 to 1.5) The molar ratio of bulk IV to Pd (dppf) Cl ₂ is 1: (0.01-0.05), and the molar ratio of intermediate IV to potassium acetate is 1: (2 to 2.5).

Take reactant III-1 as an example:

Under a nitrogen atmosphere, 0.02 mol of reactant II-1 and 0.03 mol of raw material IV-1 were weighed out and dissolved in 100 mL of toluene. 0.0002 mol of Pd ₂ (dba) ₃ 0.0008 mol of P (Ph) ₃ 0.03 mol was added. The sodium tert-butoxide was heated to 110 ° C for 24 hours. After the reaction was completed, the reaction solution was cooled and the reaction solution was filtered. The filtrate was spin-evaporated and passed through a silica gel column to obtain intermediate IV-1.

Under a nitrogen atmosphere, 0.02 mol of intermediate IV-10.04 mol of bis (pinacol) diboron 0.0002 mol of Pd (dppf) Cl ₂ 0.04 mol of potassium acetate was dissolved in 100 mL of toluene, heated to 120 ° C., and reacted 16 The sample was spotted and the reaction was completed. The reaction was cooled and filtered naturally. The filtrate was spin-evaporated to obtain the crude product. The reactant III-1 was obtained by passing through a neutral silica gel column. The purity was 95.25% and the yield was 87.5%. 441.1900, the measured value is 441.1929.

The required raw materials for the synthesis of reactant I in the examples are shown in Table 1:

Table 1

Example 4: Synthesis of Compound 1:

In a 250 ml three-necked flask, add 0.01 mol of reactant I-1, 0.012 mol of reactant II-1, and 150 ml of toluene under nitrogen protection, then add 5 × 10 ^-5 molPd ₂ (dba) ₃ , 5 × 10 ^-5 mol P (t-Bu) ₃ , 0.03 mol sodium tert-butoxide, heated to 105 ° C., and reacted under reflux for 24 hours. Sampling point plate showed no bromide remaining, the reaction was complete; naturally cooled to room temperature, filtered, and filtrate Rotate to no fractions and pass through a neutral silica gel column to obtain the target product. The purity by HPLC is 99.66% and the yield is 75.3%. HRMS (EI): The molecular weight of the material is 735.2926, and the measured molecular weight is 735.2949.

Example 5: Synthesis of compound 7:

The method for preparing compound 7 is the same as that in Example 4. The difference is that reactant I-2 is used to replace reactant I-1, and reactant II-2 is used to replace reactant II-1. The HPLC purity of the obtained target product is 99.68%, and the yield is It is 79.2%, HRMS (EI): calculated value is 927.4808, and measured value is 927.4856.

Example 6: Synthesis of compound 8:

Compound 8 was prepared in the same manner as in Example 4, except that reactant I-2 was used to replace reactant I-1 and reactant II-3 was used to replace reactant II-1. The target product was obtained with a purity of 99.80% and a yield of 74.3. %. HRMS (EI): The calculated value is 887.4491, and the measured value is 887.4408.

Example 7: Synthesis of Compound 24:

The method for preparing compound 24 is the same as that in Example 4, except that the reactant I-2 is used to replace the reactant I-1, and the reactant II-4 is used to replace the reactant II-1. The HPLC purity of the obtained target product is 97.67%, and the yield is 85.1%, HRMS (EI): Calculated 887.4491, Measured 887.4458.

Example 8: Synthesis of Compound 31:

Compound 31 was prepared in the same manner as in Example 4, except that reactant I-3 was used to replace reactant I-1, and reactant II-2 was used to replace reactant II-1. The HPLC purity of the obtained target product was 98.66%, and the yield was It was 84.5%, HRMS (EI): The calculated value was 927.4804, and the measured value was 927.4858.

Example 9: Synthesis of Compound 32:

Compound 32 was prepared in the same manner as in Example 4, except that reactant I-4 was used to replace reactant I-1, and reactant II-3 was used to replace reactant II-1. The HPLC purity of the obtained target product was 97.36%, and the yield was It was 83.5%, HRMS (EI): the calculated value was 887.4491, and the measured value was 887.4429.

Example 10: Synthesis of Compound 52:

Compound 52 was prepared in the same manner as in Example 4, except that reactant I-2 was used to replace reactant I-1, and reactant II-5 was used to replace reactant II-1. The HPLC purity of the obtained target product was 98.12% with a yield. It was 79.6%, HRMS (EI): The calculated value was 847.4178, and the measured value was 847.4191.

Example 11: Synthesis of Compound 71:

Compound 71 was prepared in the same manner as in Example 4 except that reactant I-5 was used to replace reactant I-1 and reactant II-6 was used to replace reactant II-1. The HPLC purity of the obtained target product was 95.12% and the yield was 95.12%. It is 79.5%, HRMS (EI): Calculated value is 749.2719, and measured value is 749.2734.

Example 12: Synthesis of Compound 72:

Compound 72 was prepared in the same manner as in Example 4, except that reactant I-6 was used to replace reactant I-1, and reactant II-7 was used to replace reactant II-1. The HPLC purity of the obtained target product was 96.18%, and the yield was It was 79.5%, HRMS (EI): the calculated value was 775.2875, and the measured value was 775.2821.

Example 13: Synthesis of Compound 80:

Compound 80 was prepared in the same manner as in Example 4, except that reactant I-7 was used to replace reactant I-1 and reactant II-3 was used to replace reactant II-1. The HPLC purity of the obtained target product was 99.12%, and the yield was It was 79.5%, HRMS (EI): the calculated value was 801.3396, and the measured value was 801.3358.

Example 14: Synthesis of Compound 92:

Compound 92 was prepared in the same manner as in Example 4, except that reactant I-8 was used to replace reactant I-1, and reactant II-8 was used to replace reactant II-1. The HPLC purity of the obtained target product was 97.70%, and the yield was It is 85.1%, HRMS (EI): The calculated value is 906.3610, and the measured value is 906.3625.

Example 15: Synthesis of Compound 116:

Compound 116 was prepared in the same manner as in Example 4, except that reactant I-3 was used to replace reactant I-1, and reactant II-9 was used to replace reactant II-1. The HPLC purity of the obtained target product was 94.68% with a yield. It was 88.2%, HRMS (EI): The calculated value was 875.3763, and the measured value was 875.3766.

Example 16: Synthesis of Compound 123:

The method for preparing compound 123 is the same as that in Example 4. The difference is that the reactant I-9 is used to replace the reactant I-1, and the reactant II-7 is used to replace the reactant II-1. The purity of the obtained target product is 98.56%, and the yield is 73.9%, HRMS (EI): The calculated value is 775.2875, and the measured value is 775.2829.

Example 17: Synthesis of Compound 130:

Compound 130 was prepared in the same manner as in Example 4, except that reactant I-9 was used to replace reactant I-1, and reactant II-3 was used to replace reactant II-1. The purity of the obtained target product was 97.12%, and the yield was 84.3%, HRMS (EI): The calculated value is 801.3396, and the measured value is 801.3337.

Example 18: Synthesis of Compound 143

In a 250 ml three-necked flask, add 0.01 mol of Intermediate I-10.015 mol of Intermediate III-1 and dissolve in a mixed solvent of toluene and ethanol with a volume ratio of 2: 1; under an inert atmosphere, add 0.02 mol Na ₂ CO ₃ aqueous solution (2M) 0.0001mol Pd (PPh ₃ ) ₄ ; The mixed solution of the above reactants was reacted at a reaction temperature of 95 to 110 ° C. for 10 to 24 hours. The reaction solution was cooled and filtered, and the filtrate was spin-evaporated and passed through a silica gel column. The target product was obtained with a purity of 99.80% and a yield of 74.3%. HRMS (EI): The calculated value is 811.3239, and the measured value is 811.3208.

Example 19: Synthesis of Compound 146

Compound 146 was prepared in the same manner as in Example 18, except that reactant I-2 was used to replace reactant I-1 and reactant III-2 was used to replace reactant III-1. The purity of the obtained target product was 98.12%, and the yield was 86.2%, HRMS (EI): The calculated value is 963.4804, and the measured value is 963.4837.

The compound of the present invention is used in a light emitting device, and can be used as an electron blocking layer material or a hole transporting layer material. The compounds prepared in the above examples of the present invention were respectively tested for the thermal performance T1 level HOMO level, and the test results are shown in Table 2.

Table 2

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 thermal weight loss temperature Td is the temperature at which the weight loss is 1% in a nitrogen atmosphere. Measured on Shimadzu's TGA-50H thermogravimetric analyzer. The nitrogen flow rate is 20 mL / min. The triplet energy level T1 is tested by Hitachi's F4600 fluorescence spectrometer. The test condition of the material is 2 * 10-5 toluene Solution; the highest occupied molecular orbital HOMO energy level and the lowest occupied molecular orbital LUMO energy level were tested by a photoelectron emission spectrometer (AC-2 type PESA) and tested for the atmospheric environment;

The hole mobility is measured by the linear carrier boosting method. The measurement steps are as follows:

The sample is prepared into a single-charged device, and then a positive periodic pulse is applied to the single-charged device to linearly increase the voltage. While the voltage linearly increases, the carriers in the single-charged device are instantaneously extracted. The voltage duration must be greater than or equal to The more the carrier degree is over time, the single-charged device has an initial current in the equilibrium state, and the transient current changes with time as the linear boost signal increases. When the change current reaches the maximum value, the carrier is completely extracted. The time required for the process is t _max . Finally, according to the formula:

The magnitude of the carrier mobility is calculated, t _max is the time when the change current reaches its maximum value, d is the measured thickness, A is the slope of the linear boost signal, and μ is the mobility.

It can be known from the data in Table 2 that the organic compound of the present invention has a high glass transition temperature, which can improve the phase stability of the material film, and further improve the service life of the device; with an appropriate T1 energy level, it can block the energy loss of the light-emitting layer, thereby improving the device's light Efficiency; a suitable HOMO energy level can solve the problem of carrier injection, which can reduce the device voltage; higher hole mobility can reduce the device voltage, and expand the exciton attachment region, thereby increasing the life of the OLED device. Therefore, the compound with the triarylamine core of the present invention can effectively improve the luminous efficiency and service life of the device after being applied to the hole transport layer of the OLED device. In the following, device examples 1-16 and device comparative example 1 are used to describe in detail the application effect of the compound synthesized by the present invention as a hole transport layer in a device. Device Example 2-16 and Device Comparative Example 1 Compared with Device Example 1, the manufacturing process of the device is exactly the same, and the same substrate material and electrode material are used, and the film thickness of the electrode material remains the same. The difference is that the hole transport layer or the electron blocking layer in the device is changed. The device stack structure is shown in Table 3, and the performance test results of each device are shown in Table 4 and Table 5.

Device Example 1

As shown in FIG. 1, the device embodiment uses ITO as the anode, Al as the cathode, CBP and Ir (ppy) 3 mixed at a weight ratio of 90:10 as the material of the light-emitting layer, and HAT-CN as the material of the hole injection layer. The compound 1 prepared in the example is used as a hole transport layer, TPBI is used as an electron transport layer material, and LiF is used as an electron injection layer material. The specific production steps are as follows:

Clean the ITO anode layer 2 on the transparent substrate layer 1, ultrasonically clean each with deionized water, acetone, ethanol for 15 minutes, and then process in a plasma cleaner for 2 minutes;

On the ITO anode layer 2, a hole injection layer material HAT-CN was evaporated by a vacuum evaporation method to a thickness of 10 nm, and this layer was used as the hole injection layer 3;

On the hole injection layer 3, the compound 1 prepared by the embodiment of the invention of the hole transport layer material is evaporated by vacuum evaporation, and the thickness is 60 nm. This layer is the hole transport layer 4;

On the hole transport layer 4, an electron blocking material TCTA is deposited by a vacuum evaporation method to a thickness of 20 nm, and this layer is an electron blocking layer 5;

The light-emitting layer 6 is vapor-deposited on the electron blocking layer 5, the host material is CBP, the doping material is Ir (ppy) 3, the mass ratio of CBP and Ir (ppy) 3 is 9: 1, and the thickness is 30nm;

On top of the light-emitting layer 6, a hole blocking / electron transporting material TPBI is deposited by vacuum evaporation with a thickness of 40 nm. This layer of organic material is used as the hole blocking / electron transporting layer 7;

Above the hole-blocking / electron-transport layer 7, a vacuum-deposited electron injection layer LiF having a thickness of 1 nm is used as the electron injection layer 8;

On the electron injection layer 8, a cathode Al (100 nm) is vacuum-evaporated, and this layer is a cathode reflective electrode layer 9.

After completing the fabrication of the electroluminescent device according to the above steps, the IVL data and light decay lifetime of the device were measured. The results are shown in Table 4. The molecular structure formula of the related materials is as follows:

table 3

Table 4

From the device data results in Table 4, it can be seen that the organic light-emitting device of the present invention has achieved a greater improvement in efficiency and lifetime compared to OLED devices of known materials.

In order to compare the efficiency attenuation of different devices under high current density, the efficiency attenuation coefficient φ is defined and expressed. It indicates the difference between the maximum efficiency μ100 of the device and the maximum efficiency μm of the device when the driving current is 100mA / cm ² and the maximum efficiency. The larger the value of φ, the more serious the efficiency roll-off of the device. On the contrary, it indicates that the problem of rapid degradation of the device under high current density has been controlled. For the device examples 1-16 and comparative example 1, the efficiency attenuation coefficient φ was measured, and the test results are shown in Table 5:

table 5

Device code	Efficiency attenuation coefficient φ	Device code	Efficiency attenuation coefficient φ
Device Example 1	0.22	Device Example 10	0.22
Device Embodiment 2	0.20	Device Embodiment 11	0.20
Device Embodiment 3	0.25	Device Embodiment 12	0.22
Device Example 4	0.19	Device Embodiment 13	0.23
Device Example 5	0.21	Device Embodiment 14	0.20
Device Example 6	0.22	Device Embodiment 15	0.23
Device Example 7	0.19	Device Embodiment 16	0.21
Device Embodiment 8	0.24	Comparative Example 1	0.40
Device Embodiment 9	0.22	Zh	Zh

From the data in Table 5, by comparing the efficiency attenuation coefficients of device examples 1-16 and comparative example 1, we can see that the organic light emitting device of the present invention can effectively reduce the efficiency roll-off.

Further, the efficiency of the OLED device prepared by the material of the present invention is relatively stable at low temperatures. Device Example 1413 and Device Comparative Example 1 were tested for efficiency in the range of -10 to 80 ° C. .

Table 6

As can be seen from the data in Table 6 and Figure 2, Device Example 1413 is a device structure with materials of the present invention and known materials. Compared with Device Comparative Example 1, not only the high-temperature efficiency is high, but the efficiency is stable during the temperature rise Rise.

Claims (8)

1. A triarylamine-based compound is characterized in that the structure of the compound is shown by the general formula (1):

   

   The m and n are independently taken as 0 or 1, and m and n are not 0 at the same time;

   Said a is represented by the number 0, 1, 2, 3 or 4;

   The A is a structure represented by the general formula (2), the general formula (3), the general formula (4), the general formula (5), or the general formula (6);

   

   In the general formula (3), X ₁ and X ₂ are each independently represented as -O-, -S-, -C (R ₆ ) (R ₇ )-or -N (R ₈ )-;

   The general formula (2) may be linked in parallel with the general formula (1) through a C _L1 -C _L2 bond, a C _L2- C _L3 bond or a C _L3 -C _L4 bond; the general formula (3) may be connected through a C _L5 -C _L6 bond, C _L6 -C _L7 bond or C _L7 -C _L8 bond is connected in parallel with the general formula (1); the general formula (4) can be combined with the general formula (1) through the C _L9 -C _L10 bond. Ring connection; the general formula (5) may be connected in parallel with the general formula (1) through a C _L11 -C _L12 bond; the general formula (6) may be connected through a C _L13 -C _L14 bond, or a C _L14 -C _L15 bond Or the C _L15 -C _L16 bond is connected in parallel with the general formula (1);

   The Ar ₁ and Ar ₂ are each independently represented as a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted pyridine group base;

   The R ₁ and R ₂ are each independently represented by a structure represented by the general formula (7):

   

   R ₃ and R ₄ are each independently represented as -KR ₅ ; K is represented as a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted Or unsubstituted pyridinyl; R ₅ is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted phenyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted Isoquinolinyl, substituted or unsubstituted diazaphenanthryl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, structure represented by general formula (8) or general formula (9);

   

   X ₃ , X ₄ , and X ₅ are each independently represented as a single bond, -O-, -S-, -C (R ₉ ) (R ₁₀ )-, or -N (R ₁₁ )-; and X ₃ , X _{4 is} not expressed as a single bond at the same time;

   The Z is represented by N or CR ₁₂ ;

   The group Z bonded to the group K represents a carbon atom;

   The R represents a hydrogen atom, a cyano group, a halogen, a C ₁ -C ₁₀ linear alkyl group, a C ₃ -C ₁₀ branched alkyl group, a substituted or unselected C _6-30 aryl group, containing one or more 5- to 30-membered heteroaryl substituted or unsubstituted with a heteroatom or a structure represented by the general formula (7); R may replace any substitutable site in the structure of the general formula (1); In the structure shown by), R does not represent the structure shown by general formula (7);

   The R ₆ to R ₁₁ are each independently represented as a C _1-10 alkyl group, a substituted or unsubstituted C _6-30 aryl group, and a substituted or unsubstituted 5 to 30 membered heterocyclic group containing one or more heteroatoms. One of aryl groups; wherein R ₆ and R ₇ , R ₉ and R ₁₀ may be connected to form a 5- to 30-membered alicyclic or aromatic ring;

   The R ₁₂ represents a hydrogen atom, halo, cyano, C _1-10 alkyl, C _1-10 olefin group, a substituted or unsubstituted C _6-30 aryl group containing one or more heteroatoms One of substituted or unsubstituted 5- to 30-membered heteroaryl groups; two or more adjacent R ₁₂ may be connected to form a 5- to 30-membered alicyclic or aromatic ring;

   The substituted C _6-30 aryl group and the substituted 5- to 30-membered heteroaryl group may be optionally selected from halogen, cyano, C _1-20 alkyl, C _6-20 aryl, containing one or more One or more of a 5-30 membered heteroaryl group of a heteroatom;

   The heteroatom is selected from an oxygen atom, a sulfur atom, or a nitrogen atom.
2. The compound according to claim 1, wherein the R and R ₁₂ are each independently represented by a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a tertiary group. Butyl, pentyl, phenyl, biphenyl, terphenyl, naphthyl, pyridyl or furyl;

   The R ₆ to R ₁₁ are independently represented by methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl Group, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl;

   The substituted C _6-30 aryl group and the substituted 5- to 30-membered heteroaryl group may optionally be a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a tert-butyl group. One or more of a radical, pentyl, phenyl, biphenyl, naphthyl, pyridyl, or furyl.
3. The compound according to claim 1, wherein the general formula (3) can be represented as the following structure:

   
4. The compound according to claim 1, wherein in the general formula (7), R3 and R4 can be represented as the following structures:

   
5. The compound according to claim 1, wherein the general formula (1) can be represented as the following specific structure:

   

   

   

   

   

   

   

   

   One of them.
6. An organic electroluminescent device includes a cathode, an anode, and a plurality of organic functional layers, wherein at least one organic functional layer contains the compound according to any one of claims 1-5.
7. The organic electroluminescent device according to claim 6, wherein the organic functional layer is a hole transport layer or an electron blocking layer.
8. A lighting or display element, comprising the organic electroluminescence device according to claim 6 or 7.

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