阅读说明：本技术 一种有机化合物及使用该化合物的有机光电元件 (Organic compound and organic photoelectric element using same ) 是由 高春吉 叶绪兵 王子兴 廖张程 吴空物 于 2021-06-10 设计创作，主要内容包括：本发明提供一种有机化合物和使用该化合物的有机发光器件,有机化合物结构如式1所示：Ar-(1、)R-1、R-2、L、X通过参照本文中提供的具体描述进行理解；本发明的有机化合物应用于有机电致发光二极管的功能层中,尤其是作为发光层的主体材料,使发光元件的电流效率提升,使用寿命延长,具有很好的商业化前景。(The invention provides an organic compound and an organic light-emitting device using the same, wherein the structure of the organic compound is shown as formula 1: Ar 1、 R 1 、R 2 l, X are understood by reference to the detailed description provided herein; the organic compound is applied to a functional layer of an organic electroluminescent diode, and is particularly used as a main material of a light-emitting layer, so that the current efficiency of a light-emitting element is improved, and the service life of the light-emitting element is prolongedProlonged and has good commercialization prospect.)

1. An organic compound characterized by: the structural formula is shown as 1:

in the above structural formula, Ar₁Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C10-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C4-C30 heteroaryl, substituted or unsubstituted fluorene derivative;

R₁and R₂Is substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C4-C30 heteroaryl, substituted or unsubstituted C13-C30 fluorene derivative;

l is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C4-C30 heteroaryl, substituted or unsubstituted C13-C30 amine derivative or fluorene derivative;

x represents Sulfur Oxide (SO) or sulfur dioxide (SO)₂)。

2. An organic compound characterized by: the structural formula is shown as formula 1-1 or formula 1-2:

in the above structural formula, Ar₁Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C10-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted fluorene derivative;

R₁and R₂Is substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 fluorene derivative;

l is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 amine derivative or fluorene derivative.

3. An organic compound according to claim 1 or 2, wherein Ar is₁Independently selected from one of the following structures:

wherein R is₅、R₆And R₇Independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or a combination thereof;

L₁is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 amine derivative or fluorene derivative.

4. An organic compound according to claim 1 or 2, wherein R is₁And R₂Independently selected from one or a combination of the following structures,

wherein R is₈、R₉、R₁₀Independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or the combination thereof;

L₂is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl.

5. The organic compound of any one of claims 1 to 4, wherein the organic compound is independently selected from the group consisting of:

6. an organic photoelectric element, wherein the organic photoelectric element is an organic electroluminescent device, the light-emitting device comprises an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode, and the organic compound according to any one of claims 1 to 5 is used as a host material of the light-emitting layer.

7. The organic photoelectric element according to claim 6, wherein the organic compound according to any one of claims 1 to 5 is used alone or in combination with other compounds.

8. The organic photoelectric element according to claim 6, wherein the compound according to any one of claims 1 to 5 is used as a light-emitting layer or an active layer.

9. The organic photoelectric element according to claim 6, wherein the compound according to any one of claims 1 to 5 is used as a hole-blocking layer.

10. The organic photovoltaic element according to claim 6, wherein the compound according to any one of claims 1 to 5 is used as an electron transporting layer.

Technical Field

The present invention relates to an organic compound and an organic light emitting tube device using the same, and more particularly, to a soluble organic compound having excellent color purity and high luminance and light emitting efficiency and an OLED device using the same.

Background

With the development of multimedia technology and the increase of information-oriented requirements, the requirements for the performance of panel displays are increasing. The OLED has a series of advantages of autonomous light emission, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, is widely noticed due to potential application in new-generation displays and lighting technologies, and has a very wide application prospect. The organic electroluminescent device is a spontaneous light emitting device, and the OLED light emitting mechanism is that under the action of an external electric field, electrons and holes are respectively injected from a positive electrode and a negative electrode and then migrate, recombine and attenuate in an organic material to generate light. A typical structure of an OLED comprises one or more functional layers of a cathode layer, an anode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a hole transport layer, a hole injection layer and an organic light emitting layer.

Although the research on organic electroluminescence is rapidly progressing, there are still many problems to be solved, such as the improvement of External Quantum Efficiency (EQE), the design and synthesis of new materials with higher color purity, the design and synthesis of new materials with high efficiency electron transport/hole blocking, and the like. For the organic electroluminescent device, the luminous quantum efficiency of the device is the comprehensive reflection of various factors and is an important index for measuring the quality of the device.

Luminescence can be divided into fluorescence and phosphorescence. In fluorescence emission, an organic molecule in a singlet excited state transits to a ground state, thereby emitting light. On the other hand, in phosphorescence, organic molecules in a triplet excited state transition to a ground state, thereby emitting light.

At present, some organic electroluminescent materials have been commercially used due to their excellent properties, but as host materials in organic electroluminescent devices, it is more important to have good hole transport properties in addition to the triplet energy level higher than that of the guest materials to prevent the energy reverse transfer of exciton transition release. Currently, materials having both a high triplet level and good hole mobility in the host material are still lacking. Therefore, how to design a new host material with better performance is a problem to be solved by those skilled in the art.

Disclosure of Invention

An object of the present invention is to provide an organic compound having excellent pure chromaticity, high luminance and excellent luminous efficiency, and an organic light emitting device using the same

The invention provides an organic compound, the structural formula of which is shown as 1,

in the above structural formula, Ar₁Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C10-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted fluorene derivative;

R₁and R₂Is substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 fluorene derivative;

l is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 amine derivative or fluorene derivative;

x represents Sulfur Oxide (SO) or sulfur dioxide (SO)₂)。

Preferably, an organic compound characterized by: the structural formula is shown as formula 1-1 or 1-2:

in the above structural formula, Ar₁Each independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C10-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted fluorene derivative;

R₁and R₂Is substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 fluorene derivative;

l is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 amine derivative or fluorene derivative;

further preferably, Ar in the structure of the organic compound is Ar₁Independently selected from the following structures, but not represented as being limited thereto:

wherein R is₅、R₆And R₇Independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or a combination thereof;

L₁is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C13-C30 amine derivative or fluorene derivative.

In a more preferred embodiment, R in the structure of the organic compound is₁And R₂Independently selected from the following structures, but not represented as being limited thereto:

wherein R is₈、R₉、R₁₀Independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or the combination thereof;

L₂is a single bond or is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C10-C30 condensed ring group, and substituted or unsubstituted C3-C30 heteroaryl.

In a further preferred mode, the organic compound is independently selected from one of the following compounds, but does not represent a limitation thereto:

the invention also provides application of the heterocyclic series-containing compound in an organic light-emitting device.

Preferably, the organic light emitting device comprises an anode, a cathode and a plurality of organic functional layers positioned between the anode and the cathode, wherein the organic functional layers contain the compound containing the heterocyclic series.

The invention has the beneficial effects that:

the invention provides a heterocyclic series-containing compound, which has a structure shown in a formula 1, wherein the electron-rich structure in the heterocyclic series-containing compound has great influence on the photoelectric property of the whole compound molecule, thereby being beneficial to reducing unnecessary vibration energy loss and realizing high-efficiency luminous performance. By adjusting substituent groups, the compound has better thermal stability and chemical properties. The heterocyclic series-containing compound disclosed by the invention is simple in preparation method, easily available in raw materials and capable of meeting the industrial requirements.

The heterocyclic series compounds are prepared into devices, particularly used as main materials of organic electroluminescent devices, the devices have the advantages of low driving voltage and high luminous efficiency, and are superior to the conventional common OLED devices.

In the present invention, the organic electroluminescent device preferably includes an anode, a cathode, and several organic layers located between the anode and the cathode, and the "organic layer" refers to a term of all layers disposed between the anode and the cathode in the organic electroluminescent device. The organic layer may be a layer having a hole characteristic and a layer having an electron characteristic. For example, the organic layer includes one or more of a hole injection layer, a hole transport layer, a technical layer having both hole injection and hole transport, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a technical layer having both electron transport and electron injection.

In the present invention, the hole injection layer, the hole transport layer, and the functional layer having both hole injection and hole transport properties may be formed using a conventional hole injection material, a hole transport material, or a material having both hole injection and hole transport properties, and may further include an electron-generating material.

For example, the organic layer includes a light emitting layer, and the light emitting layer includes one or more of a phosphorescent host, a fluorescent host, a phosphorescent dopant, and a fluorescent dopant. In the present invention, the compound for an organic electroluminescent device can be used as a fluorescent host, as a fluorescent dopant, and as both a fluorescent host and a fluorescent dopant.

In the present invention, the light emitting layer may be a red, yellow or blue light emitting layer. In the present invention, when the light-emitting layer is a light-emitting layer, an organic electroluminescent device having high efficiency, high resolution, high luminance and long life can be obtained by using the above-mentioned compound for an organic electroluminescent device as a host.

In the present invention, the organic electroluminescent diode device of the organic compound is characterized in that the organic electroluminescent diode device comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode, which are sequentially deposited, and the organic compound is used as a host material of the light emitting layer.

The method for preparing the organic electroluminescent device is not particularly limited, and the organic electroluminescent device can be prepared by using the method and materials for preparing the light emitting device, which are well known to those skilled in the art, in addition to the organic compound of formula 1.

Detailed Description

In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further described with reference to the figures and the specific embodiments.

Example 1: synthesis of Compounds 1-38

1. Synthesis of intermediate 1-38-1

A250 mL three-necked flask was charged with intermediate 3-bromo-10H-phenothiazine (5.56g, 20mmol), bis ([1,1' -biphenyl ] -4-yl) amine (6.75g,21.0mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (3.8g,33.6mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product, which was then subjected to silica gel column to obtain Compound 1-38-1(8.30g, yield 80%). LC-MS: M/Z518.2 (M +).

2. Synthesis of intermediate 1-38-2

A250 mL three-necked flask was charged with intermediate 1-38-1(10.37g, 20mmol), 2-chloro-4-phenylquinazoline (5.62g,21.0mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (3.8g,33.6mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product, which was then subjected to silica gel column to obtain Compound 1-38-2(11.85g, yield 79%). LC-MS: M/Z723.2 (M +).

3. Synthesis of Compounds 1-38

A250 ML three-necked flask was charged with intermediates 1-38-2(14.46g, 20mmol), dichloromethane (200ML), MCPBA (12.08, 70 mmol). The reaction system is heated to 40 ℃ and reacts for 3 hours under stirring. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give crude product, which was then subjected to silica gel column to obtain compounds 1 to 38(12.83g, yield 85%). LC-MS: M/Z754.2 (M +).

Example 2: synthesis of Compounds 1-94

1. Synthesis of intermediate 1-94-1

A500 mL reaction flask was charged with intermediate phenothiazineboronic acid ester (19.97g,61.4mmol), 4-bromo-N, N-diphenylaniline (19.1g,61.4mmol), tetrakis (triphenylphosphine) palladium (5 mol%), K₂CO₃(17.0g,122.8mmol), 1, 4-dioxane (200mL) and water (50 mL). The reaction system is heated to 80 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product, which was then passed through a silica gel column to obtain intermediate 1-94-1(20.38g, yield 75%). LC-MS: M/Z442.15(M +).

2. Synthesis of intermediates 1-94-2

A250 mL three-necked flask was charged with intermediate 1-94-1(8.85g, 20mmol), 2-chloro-4-phenylquinazoline (5.62g,21.0mmol), tris (dibenzylideneacetone) dipalladium (4 mol%), tri-tert-butylphosphine (8 mol%), potassium tert-butoxide (3.8g,33.6mmol) and o-xylene (80 mL). The reaction system is heated to 120 ℃ and reacts for 12 hours under the protection of nitrogen. After completion of the reaction, the reaction solution was cooled to room temperature and extracted with o-dichlorobenzene and water. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized to give a crude product, which was then passed through a silica gel column to obtain Compound 1-94-2(9.83g, yield 76%). LC-MS: M/Z646.22(M +).

3. Synthesis of Compounds 1-94

Compounds 1 to 94 were synthesized by the method of reference example 1 to obtain compounds 1 to 94(14.65g, yield 80%). LC-MS: M/Z678.21(M +).

Example 3: synthesis of Compounds 3-38

Compounds 3-38 were synthesized by the method of reference examples 1-38 to give compounds 3-389.81g, yield 65%). LC-MS: M/Z754.24(M +).

Example 4: synthesis of Compounds 4-38

Compounds 4 to 38 were synthesized by the method described in reference to examples 1 to 38 to obtain compounds 4 to 38(11.26g, yield 72%). LC-MS: M/Z781.25(M +).

Example 5: synthesis of Compound 5-2

Compound 5-2 was synthesized by the method of reference example 1 to give compound 5-2(13.73g, yield 80%). LC-MS: M/Z857.28(M +).

Evaluation example 1: HOMO, LUMO, triplet energy level, and S1-T1 energy level evaluation of the compounds:

the above data show that the delayed fluorescence property (S) after introduction of the amine series compound is obtained after introduction of the amine series compound into the compound₁-T₁) And (5) reinforcing.

Device embodiments

(I) Evaluation of luminescent Material devices

The compounds of the respective organic layers used in the device examples are as follows:

1. first embodiment

The ITO glass substrate was patterned to have a light-emitting area of 3mm × 3 mm. The patterned ITO glass substrate was then washed.

The substrate is then placed in a vacuum chamber. The standard pressure was set at 1X 10-6 Torr. Thereafter on an ITO substrate Compound (I)Andthe sequence of (a) and (b) forming layers of organic material.

2. Comparative example 1

An organic light-emitting device of comparative example was prepared in the same manner as in the first embodiment described above, except that the host material layer of the organic light-emitting device was replaced with the compound RH-a from the compounds 1 to 38 of the first embodiment.

The prepared organic light-emitting device is at 10mA/cm²Voltage, efficiency and life were tested under current conditions.

Table 1 shows the performance test results of the organic light emitting devices prepared in the examples of the present invention and the comparative examples.

As shown in table 1, the device also operated efficiently at the same voltage. And the current efficiency and lifetime of the embodiment are significantly increased compared to the comparative example, for example, the performance of the device is significantly improved after introducing the (S ═ O) group when comparing example 1 and comparative example 1, example 3 and comparative example 2, example 4 and comparative example 3, and example 5 and comparative example 4.

The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.