阅读说明：本技术 一种含螺芴蒽酮结构的有机化合物及其应用 (Organic compound containing spirofluorene anthrone structure and application thereof ) 是由 李崇 吴秀芹 张兆超 王芳 庞羽佳 于 2018-06-27 设计创作，主要内容包括：本发明公开了一种含螺芴蒽酮结构的有机化合物及其应用,本发明化合物中π共轭效应使得其有很强的空穴传输能力,高的空穴传输速率能够降低器件的起始电压,提高有机电致发光器件的效率；且其中不对称的三芳胺结构能够降低分子的结晶性和平面性,阻止分子在平面上移动,从而提高分子的热稳定性；同时,本发明提供的化合物的结构使得电子和空穴在发光层的分布更加平衡,在恰当的HOMO能级下,提升了空穴注入和传输性能；在合适的LUMO能级下,又起到了电子阻挡的作用,提升激子在发光层中的复合效率。(The invention discloses an organic compound containing a spirofluorene anthrone structure and application thereof, wherein pi conjugated effect in the compound enables the compound to have strong hole transmission capability, and the high hole transmission rate can reduce the initial voltage of a device and improve the efficiency of an organic electroluminescent device; the asymmetric triarylamine structure can reduce the crystallinity and the planarity of molecules and prevent the molecules from moving on a plane, so that the thermal stability of the molecules is improved; meanwhile, the structure of the compound provided by the invention enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons and improves the recombination efficiency of excitons in the light-emitting layer.)

1. An organic compound containing a spirofluorene anthrone structure is characterized in that the structure of the organic compound is shown as a general formula (1):

in the general formula (1), R is₁、R₂、R₃、R₄Each independently represents a hydrogen atom, a halogen, a cyano group, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted C_6-60An aryl group, a substituted or unsubstituted 5-to 60-membered heteroaryl group containing one or more heteroatoms, or a structure of formula (2); r₁、R₂、R₃、R₄Are respectively connected with the framework structure in the general formula (1) through a single bond or a benzo ring structure; and R is₁、R₂、R₃、R₄At least one of the structures represented by the general formula (2);

in the general formula (2), L represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group;

said L₁、L₂Represents a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene;

R₅、R₆represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a structure shown in a general formula (3) or a general formula (4);

said X₁、X₂Each independently represents a single bond, -O-, -S-, -C (R)₈)(R₉) -or-N (R)₁₀)-；

Said L₁、L₂Represented by substituted or unsubstituted phenylene, substituted or unsubstituted phenyleneBiphenyl, substituted or unsubstituted naphthylene; l is₁Also represents a single bond, and when X₁And X₂Respectively represent a single bond and-N (R)₁₀) When is, L₁Represents only a single bond;

R₈～R₁₀are each independently represented by C₁-C₂₀Alkyl, substituted or unsubstituted C_6-30One of an aryl, substituted or unsubstituted 5-to 50-membered heteroaryl; the R is₈And R₉May also be linked to form a 5-to 30-membered aliphatic or aromatic ring;

the substituent is halogen, cyano, C₁-C₂₀One of the alkyl groups of (1).

2. The organic compound of claim 1, wherein R is₁、R₂、R₃、R₄Independently represents a structure represented by general formula (5) or general formula (6):

in the general formula (5), a is represented by

Said X₃、X₄、X₅Independently represent-O-, -S-, -C (R)₁₁)(R₁₂) -or-N (R)₁₃)-；

The R is₁₁～R₁₃Are each independently represented by C_1-20Alkyl, substituted or unsubstituted C_6-30One of an aryl, substituted or unsubstituted 5-to 50-membered heteroaryl; the R is₁₁And R₁₂May also be linked to form a 5-to 30-membered aliphatic or aromatic ring;

the general formula (5) and the general formula (6) are respectively connected with the skeleton structure in the general formula (1) through a form of forming a benzo ring;

the substituent is halogen, cyano, C₁-C₂₀Alkyl group of (1).

3. The organic compound according to claim 1, wherein the structure of the organic compound is any one of general formulas (I) to (VII):

4. the organic compound of claim 1, wherein R is₁、R₂、R₃、R₄Each independently represents one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a pyridyl group or a furyl group.

5. The organic compound of claims 1 and 2, wherein R is₈～R₁₃Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl; r₈And R₉、R₁₁And R₁₂And may be linked to form a 5-to 30-membered aliphatic or aromatic ring.

6. The organic compound according to claim 1, wherein the specific structure of the organic compound is:

7. An organic electroluminescent device comprising the organic compound according to any one of claims 1 to 6, comprising a light-emitting layer, wherein the light-emitting layer material contains the organic compound containing a spirofluorene anthrone structure.

8. An organic electroluminescent device comprising the organic compound according to any one of claims 1 to 6, comprising a hole transport layer/electron blocking layer, wherein the hole transport layer/electron blocking layer material contains the organic compound containing a spirofluorene anthrone structure.

9. A lighting or display element comprising the organic electroluminescent device according to any one of claims 7 to 8.

Technical Field

The invention relates to the technical field of semiconductors, in particular to an organic compound containing spirofluorene anthrone in a structure and application thereof in an organic electroluminescent device.

Background

The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.

At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.

The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials.

In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.

The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.

Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.

Disclosure of Invention

In view of the above problems in the prior art, the present applicant provides an organic compound containing a spirofluorene anthrone structure and applications thereof. The compound contains the spirofluorene anthrone structure, has higher glass transition temperature and molecular thermal stability, proper HOMO energy level and T1 energy level and high hole mobility, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.

The technical scheme of the invention is as follows:

an organic compound containing a spirofluorene anthrone structure, wherein the structure of the organic compound is shown as a general formula (1):

in the general formula (1), R is₁、R₂、R₃、R₄Each independently represents a hydrogen atom, a halogen, a cyano group, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted C_6-60An aryl group, a substituted or unsubstituted 5-to 60-membered heteroaryl group containing one or more heteroatoms, or a structure of formula (2); r₁、R₂、R₃、R₄Are respectively connected with the framework structure in the general formula (1) through a single bond or a benzo ring structure; and R is₁、R₂、R₃、R₄At least one of the structures represented by the general formula (2);

in the general formula (2), L represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted naphthylene group;

said L₁、L₂Represents a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene;

R₅、R₆represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a structure shown in a general formula (3) or a general formula (4);

said X₁、X₂Each independently represents a single bond, -O-, -S-, -C (R)₈)(R₉) -or-N (R)₁₀)-；

Said L₁、L₂Represented by substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene; l is₁Also represents a single bond, and when X₁And X₂Respectively represent a single bond and-N (R)₁₀) When is, L₁Represents only a single bond;

R₈～R₁₀are each independently represented by C₁-C₂₀Alkyl, substituted or unsubstituted C_6-30One of an aryl, substituted or unsubstituted 5-to 50-membered heteroaryl; the R is₈And R₉May also be linked to form a 5-to 30-membered aliphatic or aromatic ring;

the substituent is halogen, cyano, C₁-C₂₀One of the alkyl groups of (1).

In a preferred embodiment, the R group₁、R₂、R₃、R₄Independently represents a structure represented by general formula (5) or general formula (6):

in the general formula (5), a is represented by

Said X₃、X₄、X₅Independently represent-O-, -S-, -C (R)₁₁)(R₁₂) -or-N (R)₁₃)-；

The R is₁₁～R₁₃Are each independently represented by C_1-20Alkyl, substituted or unsubstituted C_6-30One of an aryl, substituted or unsubstituted 5-to 50-membered heteroaryl; the R is₁₁And R₁₂May also be linked to form a 5-to 30-membered aliphatic or aromatic ring;

the general formula (5) and the general formula (6) are respectively connected with the skeleton structure in the general formula (1) through a form of forming a benzo ring;

the substituent is halogen, cyano, C₁-C₂₀Alkyl group of (1).

Preferably, the structure of the organic compound is any one of general formulas (I) to (VII):

further preferably, R is₁、R₂、R₃、R₄Each independently represents one of a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a pyridyl group or a furyl group.

Further preferably, R is₈～R₁₃Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl or furyl; r₈And R₉、R₁₁And R₁₂And may be linked to form a 5-to 30-membered aliphatic or aromatic ring.

The preferred specific structure of the organic compound is:

(W81).

An organic electroluminescent device containing the organic compound comprises a light-emitting layer, and the material of the light-emitting layer contains the organic compound containing the spirofluorene anthrone structure.

An organic electroluminescent device containing the organic compound comprises a hole transport layer/electron blocking layer, and the material of the hole transport layer/electron blocking layer contains the organic compound containing the spirofluorene anthrone structure.

An illumination or display element comprising the above organic electroluminescent device.

Preferably, when the structure of the compound of the invention is shown in the general formula (I), L, R₅And R₆Has the meanings as listed in table 1 below:

TABLE 1

Compounds 41-56, which in turn have the same structure as compounds 25-40, except that R is₆Is shown as

Compounds 57-72, which in turn have the same structure as compounds 25-40, except that R is₆Is shown asCompounds 73-88, which in turn have the same structure as compounds 25-40, except that R is₆Is shown as

Compounds 89-104, which in turn have the same structure as compounds 25-40, except that R is₆Is shown as

The compound 105-120, which in turn has the same structure as the compounds 25-42, except that R is₆Is shown as

The compound 121-240, which in turn has the same structure as the compounds 1-120, except that L is represented byThe compound 241-360, which in turn has the same structure as the compounds 1-120, except that L is represented byCompound 361-465 having the same structure as compounds 1-105 in that order except that L is represented by

When the structure of the compound is shown as the general formula (II), R₁When the structure is represented by the general formula (2), the structure of the formula (II) is preferably represented by the formula (H), the formula (B), the formula (C) or the formula (D):

preferably, the compound 466-585, which in turn has the same structure as the compounds 1 to 120, except that the parent nucleus in formula (I) is replaced by the parent nucleus in formula (H);

compound 586-705, in turn, having the same structure as compounds 1-120, except that the parent nucleus in formula (I) is replaced with the parent nucleus in formula (B);

compound 706-825, in turn, having the same structure as compounds 1-120, except that the parent nucleus in formula (I) is replaced with the parent nucleus in formula (C);

compound 826-;

preferably, when the structure of formula (1) is as shown in formula (II), R₁、L、R₅And R₆Having the meanings as set forth in table 2 below, the compounds of the invention are preferably of the following structure but are not limited thereto;

TABLE 2

Note: "+" in the table indicates the attachment site;

preferred embodiment, compound 986-1001, which in turn has the same structure as compound 970-985, except that R₆Is shown as

The compound 1002-1017, which in turn has the same structure as the compound 970-985, except that R₆Is shown asCompound 1018-₆Is shown as

When the structure of the compound is shown as the general formula (III), R₁、R₂、L、R₅And R₆Having the meanings as set forth in table 3 below, the compounds of the invention are preferably of the following structure but are not limited thereto;

TABLE 3

Note: "+" in the table indicates the attachment site;

compound 1074-1089 having in turn the same structure as compound 1058-1073, except that R₆Is shown as

Compound 1090-1105 in turn having the same structure as compound 1058-1073, except that R₆Is shown as

Compound 1106-1121, which in turn has the same structure as compound 1058-1073, except that R is₆Is shown as

Preferably, when the structure of the compound is shown as the general formula (IV), the compound of the present invention is preferably, but not limited to, the following structure; in the formula (IV), L, R₅And R₆Has the following meanings as listed in table 4 below:

TABLE 4

Compound 1162-1177, which in turn has the same structure as compound 1146-1161, except that R₆Is shown as

Compound 1178-1193, which in turn has the same structure as compound 1146-1161, except that R₆Is shown as

Compound 1194-1209, which in turn has the same structure as compound 1146-1161, except that R₆Is shown as

Compound 1210-1225, which in turn has the same structure as compound 1146-1161, except that R₆Is shown as

Compound 1226-1241, which in turn has the same structure as compound 1146-1161, except that R₆Is shown as

The compound 1242-1361 which in turn has the same structure as the compound 1122-1361 except that L is represented byCompound 1362-1481 which in turn has the same structure as compound 1122-1241, with the difference that L is represented byCompound 1482-1601 which in turn has the same structure as compound 1122-1241, except that L is represented by

Preferably, when the structure of the compound is shown as the general formula (V), the compound of the present invention is preferably, but not limited to, the following structure; in the formula (V), L, R₁、R₅And R₆Has the following meanings as listed in the following table 5:

TABLE 5

Note: "+" in the table indicates the attachment site;

compound 1642-1657 having the same structure as compound 1626-1641 in that order except that R₆Is shown as

Compound 1658-₆Is shown as

Compound 1674-₆Is shown as

The invention also provides a preparation method of the organic compound containing the spirofluorene anthrone structure, which comprises the following two conditions:

(1) when L represents a single bond, the steps are as follows: under the protection of inert gas, dissolving the raw material I and the intermediate A in toluene, and adding Pd₂(dba)₃Reacting the mixed solution at 95-110 ℃ for 10-24 h, naturally cooling to room temperature, filtering, rotatably evaporating filtrate, and passing the residue through a neutral silica gel column to obtain a target product;

the reaction equation is as follows:

(2) when L does not represent a single bond, the procedure is as follows: under the protection of inert gas, dissolving the raw material I and the intermediate B by using a THF solvent, and adding K₂CO₃Aqueous solution and Pd (PPh)₃)₄Reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 h, naturally cooling to room temperature, filtering, carrying out rotary evaporation on the filtrate, and passing the residue through a silica gel column to obtain a target product;

the reaction equation is as follows:

further, the molar ratio of the raw material I to the intermediate A is 1: 1.0-1.5; the Pd₂(dba)₃The molar ratio of the raw material I to the raw material I is 0.005-0.01: 1; the molar ratio of the tri-tert-butylphosphine to the raw material I is 0.005-0.02: 1; the molar ratio of the sodium tert-butoxide to the raw material I is 1.5-3.0: 1; the molar ratio of the raw material I to the intermediate B is 1: 1-2; the volume ratio of the toluene to the ethanol is 2-2.5: 1; na (Na)₂CO₃The molar ratio of the raw material I to the raw material I is 1.0-3.0: 1; pd (PPh)₃)₄The molar ratio of the raw material I to the raw material I is 0.006-0.02: 1.

Further, the preparation of the intermediate A comprises the following steps:

weighing raw material O and raw material P, dissolving with toluene, and adding Pd₂(dba)₃、P(Ph)₃And sodium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 90-110 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate A;

the reaction equation is as follows:

further, the molar ratio of the raw material O to the raw material P is 1 (1.0-1.5); pd₂(dba)₃The molar ratio of the sodium tert-butoxide to the raw material O is (0.006-0.02): 1, and the molar ratio of the sodium tert-butoxide to the raw material O is (2.0-3.0): 1; p (Ph)₃The molar ratio of the raw material O to the raw material O is (2.0-3.0): 1;

further, the preparation of the intermediate B comprises the following steps:

(1) weighing the intermediate A and the raw material N, and dissolving the intermediate A and the raw material N in toluene; then adding Pd₂(dba)₃、P(Ph)₃Sodium tert-butoxide; reacting the mixed solution of the reactants at 95-110 ℃ for 10-24 hours under an inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate Z;

(2) weighing intermediate Z, bis (pinacolato) diboron and Pd (dppf) Cl in the atmosphere of nitrogen₂Dissolving potassium acetate in toluene, reacting for 12-24 hours at 100-120 ℃, sampling a sample, completely reacting, naturally cooling, filtering, rotatably steaming filtrate to obtain a crude product, and passing through a neutral silica gel column to obtain an intermediate B;

the reaction equation is as follows:

further, in the step (1), the molar ratio of the intermediate A to the raw material N is 1:1.0-1.5, and Pd₂(dba)₃The molar ratio of the intermediate A to the intermediate A is 0.006-0.02: 1, P (Ph)₃The molar ratio of the sodium tert-butoxide to the intermediate A is 0.006-0.02: 1, and the molar ratio of the sodium tert-butoxide to the intermediate A is 1.0-3.0: 1;

in the step (2), the molar ratio of the intermediate Z to the bis (pinacolato) diboron is 2: 1-1.5, and the intermediate Z and Pd (dppf) Cl₂The molar ratio of the intermediate Z to the potassium acetate is 1: 0.01-0.05, and the molar ratio of the intermediate Z to the potassium acetate is 1: 2-2.5.

The beneficial technical effects of the invention are as follows:

the pi conjugation effect in the compound provided by the invention enables the compound to have strong hole transmission capability, the high hole transmission rate can reduce the initial voltage of the device, and the efficiency of the organic electroluminescent device is improved; the asymmetric triarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules and prevent the molecules from accumulating and crystallizing, thereby improving the thermal stability of the molecules; meanwhile, the structure of the compound provided by the invention enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons, and improves the recombination efficiency of excitons in the luminescent layer; when the spirofluorene anthrone serving as a light-emitting functional layer material of an OLED light-emitting device is used, the spirofluorene anthrone can be matched with the branched chain in the range of the spirofluorene anthrone so as to effectively improve the exciton utilization rate and the high fluorescence radiation efficiency, reduce the efficiency roll-off under high current density, reduce the voltage of the device, improve the current efficiency of the device and prolong the service life of the device.

When the compound is applied to an OLED device, high film stability can be kept through device structure optimization, and the photoelectric performance of the OLED device and the service life of the OLED device can be effectively improved. The compound has good application effect and industrialization prospect in OLED luminescent devices.

Drawings

FIG. 1 is a schematic diagram of the application of the compounds of the present invention to an OLED device;

in the figure, 1 is a transparent substrate layer; 2 is an ITO anode layer; 3 is a hole injection layer, 4 is a hole transport or electron blocking layer; 5 is a light-emitting layer; 6 is an electron transport or hole blocking layer; 7 is an electron injection layer; and 8, a cathode reflective electrode layer.

FIG. 2 is a graph of current efficiency measured at different temperatures for OLED devices prepared with the compounds of the present invention.

Fig. 3 is a graph showing a reverse voltage leakage current test performed on the device 19 manufactured in the comparative example 1 and the device 2 of the present invention.

Detailed Description

The present invention will be described in detail with reference to the accompanying drawings and examples.