1. An iridium complex, wherein the iridium complex has a general structural formula of formula I:

wherein m is a positive integer of not more than 3, and when m is 3, an a ring is absent; when m is 1 or 2, the ring A is a cyclic structure;

a. b and c are integers, a is more than or equal to 0 and less than or equal to 4, b is more than or equal to 0 and less than or equal to 2, and c is more than or equal to 1 and less than or equal to 4;

x is O or S, Y is N or P;

R₁、R₂and R₃Is at any position of the ring and is independently selected from at least one of hydrogen, deuterium, amino, hydroxyl, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4-30-membered aromatic heterocyclic group, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C5-C30 spiro ring; and at least one R₃Is fluorine.

2. An iridium complex according to claim 1, wherein R is₁，R₂，R₃At least one group of which forms a ring with the ring structure in which it is located.

3. The iridium complex according to claim 1, wherein the general structural formula of the iridium complex is any one of formula 01 to formula 04:

in the formula, R₄、R₅、R₆、R₇And R₈Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4-to 30-membered aromatic heterocyclic group, substituted or unsubstituted C10-C30 condensed ring group; r₇And R₈At any position of the ring;

d. e, f, g and h are integers, d is more than or equal to 0 and less than or equal to 1, e is more than or equal to 0 and less than or equal to 2, f is more than or equal to 0 and less than or equal to 2, g is more than or equal to 0 and less than or equal to 4, and h is more than or equal to 0 and less than or equal to 4.

4. An iridium complex according to claim 3, wherein R is₇And/or R₈And the ring-shaped structure with the ring-shaped structure.

5. An iridium complex according to claim 3, wherein the iridium complex has a chemical structure of any one of the following formulae:

6. a method for producing an iridium complex according to any one of claims 3 to 5, comprising the steps of:

reacting the raw material A with iridium trichloride to obtain an intermediate B;

reacting the intermediate B with the raw material C to obtain the iridium complex; or reacting the intermediate B with silver trifluoromethanesulfonate to obtain an intermediate C, and then reacting the intermediate C with the raw material D to obtain the iridium complex;

wherein the structural formulas of the raw material A and the raw material D are respectively and independently formula A-01 or formula A-02:

the structural formula of the raw material C is represented by formula C-01:

7. use of an iridium complex as claimed in any one of claims 1 to 5 in the preparation of an organic electroluminescent device.

8. An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the iridium complex as claimed in any one of claims 1 to 5.

9. An organic electroluminescent device according to claim 8, wherein the organic layer comprises a light-emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely comprises the iridium complex.

10. A display device comprising a functional module and a display module, characterized in that the display module comprises the organic electroluminescent device as claimed in claim 8 or 9.

Background

With the development of multimedia information technology, users have higher and higher requirements for the performance of display devices such as flat panels, notebooks, and the like. Compared with liquid crystal display devices, organic electroluminescent devices (OLEDs) do not need a backlight source, and have the advantages of wider viewing angle, low power consumption, high response speed and the like, so the OLEDs have wider application prospects.

Among them, the luminescent materials of OLEDs are mainly phosphorescent luminescent materials, and the metal iridium complex is a phosphorescent luminescent material which is widely studied at present. However, the conventional OLEDs using the iridium complex as a light emitting material still have the problems of high driving voltage, low light emitting efficiency, short service life, and the like.

Disclosure of Invention

An object of the embodiments of the present invention is to provide an iridium complex to solve the problems in the background art.

In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:

an iridium complex has a general structural formula of formula I:

wherein m is a positive integer of not more than 3, and when m is 3, an a ring is absent; when m is 1 or 2, the ring A is a cyclic structure;

a. b and c are integers, a is more than or equal to 0 and less than or equal to 4, b is more than or equal to 0 and less than or equal to 2, and c is more than or equal to 1 and less than or equal to 4;

x is O or S, Y is N or P;

R₁、R₂and R₃Is at any position of the ring and is independently selected from at least one of hydrogen, deuterium, amino, hydroxyl, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4-30-membered aromatic heterocyclic group, substituted or unsubstituted C10-C30 condensed ring group, substituted or unsubstituted C5-C30 spiro ring; and at least one R₃Is fluorine.

Wherein two or more substituents R in the same molecule₁、R₂And R₃May have different meanings. R₁，R₂，R₃Or can form an aromatic ring or an aromatic heterocyclic ring or a ring system with the ring on which the compound is arranged.

Specifically, the a ring may be one of a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, or an eight-membered ring. Preferably, R₁，R₂，R₃At least one group of which forms a ring with the ring structure in which it is located.

Preferably, the structural general formula of the iridium complex is any one of formula 01 to formula 04:

in the formula, R₄、R₅、R₆、R₇And R₈Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 4-to 30-membered aromatic heterocyclic group, substituted or unsubstituted C10-C30 condensed ring group; r₇And R₈At any position of the ring; r₇，R₈Or can form an aromatic ring or an aromatic heterocyclic ring or a ring system with the ring; d. e, f, g and h are integers, d is more than or equal to 0 and less than or equal to 1, e is more than or equal to 0 and less than or equal to 2, f is more than or equal to 0 and less than or equal to 2, g is more than or equal to 0 and less than or equal to 4, and h is more than or equal to 0 and less than or equal to 4. Preferably, R₇And/or R₈Form a ring knot with the ring on which it is arrangedAnd (5) forming. Preferably, the iridium complex has a chemical structural formula of any one of the following formulas:

some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of some simple groups, substituted groups and substituted positions thereof, and are not described in detail herein.

Another object of the embodiments of the present invention is to provide a preparation method of the iridium complex, which includes the following steps:

reacting the raw material A with iridium trichloride to obtain an intermediate B;

reacting the intermediate B with the raw material C to obtain the iridium complex; or reacting the intermediate B with silver trifluoromethanesulfonate to obtain an intermediate C, and then reacting the intermediate C with the raw material D to obtain the iridium complex;

wherein the structural formulas of the raw material A and the raw material D are respectively and independently formula A-01 or formula A-02:

the structural formula of the raw material C is represented by formula C-01:

specifically, the synthetic route of formula 01 is as follows:

the synthetic route for formula 02 is as follows:

the synthetic route for formula 03 is as follows:

the synthetic route for formula 04 is as follows:

another object of the embodiments of the present invention is to provide an application of the iridium complex in preparation of organic electroluminescent devices.

It is another object of an embodiment of the present invention to provide an organic electroluminescent device, including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, where the organic layer includes the iridium complex described above.

Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely comprises the iridium complex. Specifically, the iridium complex is in a single form or is mixed with other substances and exists in the organic layer. Preferably, the organic layer includes at least one or more of a hole injection layer, a hole transport layer, a layer having both hole injection and hole transport technologies, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a layer having both electron transport and electron injection technologies. Preferably, the mixing ratio of the main material to the doping material is 90: 10-99.5: 0.5. Preferably, the organic electroluminescent device may be used for an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, or an organic thin film transistor.

Another object of an embodiment of the present invention is to provide a display apparatus, including a functional module and a display module, where the display module includes the above organic electroluminescent device.

Compared with the prior art, the embodiment of the invention has the beneficial effects that: according to the iridium complex provided by the embodiment of the invention, the specific heterocyclic ligand is selected to be coordinated and combined with iridium, so that the wavelength of the iridium complex can be adjusted, and after the iridium complex is used for an organic electroluminescent device, the luminous efficiency of the organic electroluminescent device can be obviously improved, the service life of the organic electroluminescent device can be prolonged, and the driving voltage of the organic electroluminescent device can be reduced. In addition, the preparation method of the iridium complex provided by the embodiment of the invention has the advantages of simple process and high purity of the prepared product.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The iridium complexes described below are used as examples in the examples of the present invention, and the preparation methods of the other iridium complexes are similar and will not be further illustrated herein.

Example 1

This example provides an iridium complex of formula i-2, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

ligand A-2(14.57g,50mmol), IrC1 was weighed out under nitrogen protection₃·3H₂O (7.76g,22mmo1) is put into a reaction system, a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 pure water is added, the mixture is refluxed for 25 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand B-2 obtained was 9.42g in the form of a dark red powder, with a yield of 53%.

Then weighing the bridging ligand B-2(8.90g,5.5mmol), adding anhydrous potassium carbonate (7.59g,55mmol), adding 170ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-2(2.20g,22mmol) under nitrogen, refluxing for 24 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, and concentrating the filtrate to precipitate solid, thereby finally obtaining the iridium complex shown in the formula I-2, wherein the mass of the iridium complex is 3.64 g. The yield was 38% and the HPLC purity was greater than 99.5%.

Mass spectrum calculated 871.96; the test value was 871.43.

The calculated value of the elemental analysis (%) is 59.23; h is 3.81; f is 4.36; 22.04 parts of Ir; n is 3.21; o is 7.34, and the test value C is 59.25; h is 3.82; f is 4.38; 22.02 parts of Ir; n is 3.20; o is 7.32.

Example 2

This example provides an iridium complex of formula I-11, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

ligand A-11(21.07g,50mmol), IrC1 was weighed out under nitrogen protection₃·3H₂O (7.76g,22mmo1) is put into a reaction system, mixed solution of 420m1 ethylene glycol ethyl ether and 140m1 pure water is added, the mixture is refluxed for 25 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand B-11 obtained was 11.99g in the form of a dark red powder, in 51% yield.

Then weighing the bridging ligand B-11(11.75g,5.5mmol), adding anhydrous potassium carbonate (7.59g,55mmol), adding 230ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-11(3.27g,16.5mmol) under nitrogen, refluxing for 24 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, concentrating the filtrate, and precipitating a solid to obtain the iridium complex shown in the formula I-11, wherein the mass of the iridium complex is 4.33 g. The yield was 32% and the HPLC purity was greater than 99.5%.

Mass spectrum calculated 1230.39 test 1230.16.

The calculated value of the elemental analysis (%) is 66.38; h is 4.34; f is 6.18; 15.62 parts of Ir; 2.28 of N; o is 5.20, and the test value is 66.35; h is 4.32; f is 6.17; 15.65 parts of Ir; 2.28 of N; o is 5.23.

Example 3

This example provides an iridium complex of formula I-44, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

ligand A-44(25.28g,60mmol), IrC1 was weighed out under nitrogen protection₃·3H₂O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 500m1 ethylene glycol ethyl ether and 167m1 purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand B-44 was 12.61g, a dark red powder was obtained in 59% yield.

Then weighing the bridging ligand B-44(10.68g,5mmol), adding anhydrous potassium carbonate (6.9g,50mmol), adding 210ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-44(3.18g,15mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as solvent, using neutral alumina column chromatography, concentrating the filtrate, and precipitating solid to obtain iridium complex shown in formula I-44 with mass of 4.23 g. The yield was 34% and the HPLC purity was greater than 99.5%.

Mass spectrum calculated 1244.32; the test value was 1244.19.

The calculated value of the elemental analysis (%) is C: 60.81; h is 4.13; f is 12.21; 15.45 parts of Ir; 2.25 of N; o is 5.14, and the test value is C is 60.80; h is 4.10; f is 12.22; 15.43 parts of Ir; 2.28 of N; o is 5.16.

Example 4

This example provides an iridium complex of formula I-62, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

ligand A-62(14.79g,44mmol), IrC1 was weighed out under nitrogen protection₃·3H₂O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 pure water is added, reflux is carried out for 28 hours under the protection of nitrogen, then cooling is carried out to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand B-62 was 11.68g, which was obtained as a dark red powder in 65% yield.

Then weighing the bridging ligand B-62(10.78g,6mmol), adding anhydrous potassium carbonate (8.28g,60mmol), adding 210ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-62(7.21g,30mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, and concentrating the filtrate to precipitate solid, thereby finally obtaining the iridium complex shown in the formula I-62 with the mass of 5.55 g. The yield was 42% and the HPLC purity was greater than 99.5%.

Mass spectrum calculated 1102.06; the test value was 1102.40.

Elemental analysis (%): calculated value is C: 53.40; h is 3.57; f, 17.24; 17.44 parts of Ir; n is 2.54; o is 5.81, and the test value is 53.41; h is 3.59; f, 17.25; 17.44 parts of Ir; n is 2.51; o is 5.80.

Example 5

This example provides an iridium complex of formula I-83, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

weighing the formula A-83(20.06g,54mmol), IrC1 under nitrogen protection₃·3H₂O (7.05g,20mmo1) was put into the reaction system, a mixed solution of 410m1 ethylene glycol ethyl ether and 140m1 purified water was added thereto, and the mixture was refluxed for 28 hours under nitrogen protection, and then heatedCooling to room temperature, precipitating, filtering, washing with water, anhydrous alcohol, and petroleum ether, and oven drying. The mass of the bridged ligand B-83 obtained was 11.23g in the form of a dark red powder, in 58% yield.

Then weighing the bridging ligand B-83(9.68g,5mmol), adding anhydrous potassium carbonate (6.9g,50mmol), adding 200ml ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-83(4.61g,20mmol) under nitrogen, refluxing for 20 hours under nitrogen protection, cooling, filtering, washing with alcohol, and drying. Dichloromethane is used as a solvent, neutral alumina column chromatography is carried out, filtrate is concentrated, solid is precipitated, and finally the iridium complex shown in the formula I-83 is obtained, wherein the mass of the iridium complex is 3.37 g. The yield was 29% and the HPLC purity was greater than 99.5%.

Mass spectrum calculated 1162.29; the test value was 1162.53.

Elemental analysis (%): calculated value is C: 63.04; h is 4.34; f is 8.17; 16.54 parts of Ir; 2.41 of N; o is 5.51, and the test value is C is 63.06; h is 4.35; f is 8.18; 16.52 parts of Ir; 2.40 of N; o is 5.50.

Example 6

This example provides an iridium complex of formula i-96, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

weighing the formula A-96(21.26g,50mmol), IrC1 under nitrogen protection₃·3H₂O (7.05g,20mmo1) is put into a reaction system, mixed solution of 420m1 ethylene glycol ethyl ether and 140m1 purified water is added, reflux is carried out for 28 hours under the protection of nitrogen, then cooling is carried out to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The mass of the bridged ligand B-96 was 10.98g, which was obtained in the form of a dark red powder, in 51% yield.

Then weighing the bridging ligand B-96(10.76g,5mmol), adding anhydrous potassium carbonate (6.9g,50mmol), adding 210ml of ethylene glycol ethyl ether into the system, replacing nitrogen for three times, adding the formula C-96(7.05g,25mmol) under nitrogen, refluxing for 20 hours under the protection of nitrogen, cooling, filtering, washing with alcohol, and drying. Using dichloromethane as a solvent, performing chromatography by using a neutral alumina column, and concentrating the filtrate to separate out solid, thereby finally obtaining the iridium complex shown in the formula I-96 with the mass of 3.17 g. The yield was 24% and the HPLC purity was greater than 99.5%.

Mass spectrum calculated 1321.72; the test value was 1321.41.

Elemental analysis (%): calculated value is C: 39.08; h is 0.61; f, 38.81; 14.54 parts of Ir; 2.12 of N; o:4.84, test value C: 39.09; h is 0.63; 38.84 is used as a reference material; 14.52 parts of Ir; 2.11 of N; o is 4.81.

Example 7

This example provides an iridium complex of formula i-100, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

weighing formula A-100(9.31g,60mmol), IrC1 under nitrogen protection₃·3H₂O (20mmo1,7.05g) is put into a reaction system, a mixed solution of 180m1 ethylene glycol ethyl ether and 60m1 pure water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridged ligand B-100 was obtained as a yellow powder (4.61g, 43% yield).

Weighing the intermediate B-100(4.29g and 4mmol), adding silver trifluoromethanesulfonate (2.26g and 8.8mmol), adding 90ml of dichloromethane into the system, adding 30ml of methanol, refluxing for 24 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-100 was obtained as a yellow powder (5.52g, 97% yield).

Weighing the intermediate C-100(4.98g,7mmol), adding the ligand D-100(6.43g,17.5mmol), adding 100ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The filtrate was concentrated by column chromatography on silica gel using methylene chloride as solvent to give the final yellow compound of formula I-100 (1.27g, 21% yield) with an HPLC purity of greater than 99%.

Mass spectrum calculated 867.02 test 867.30.

Elemental analysis (%). calcd for C: 65.11; h is 3.84; f is 2.19; 22.17 parts of Ir; n is 4.85; o is 1.85, and the test value is 65.12; h is 3.86; f is 2.19; 22.15 parts of Ir; n is 4.85; o is 1.86.

Example 8

This example provides an iridium complex of formula I-114, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

formula A-114(14.57g,50mmol), IrC1 was weighed out under nitrogen protection₃·3H₂O (7.05g,20mmo1) is put into a reaction system, mixed solution of 290m1 ethylene glycol ethyl ether and 97m1 pure water is added, reflux is carried out for 28 hours under the protection of nitrogen, then cooling is carried out to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridged ligand form B-114 was obtained as a yellow powder (5.66g, 35% yield).

Weighing the intermediate B-114(5.66g,3.5mmol), adding silver trifluoromethanesulfonate (2.76g,10.5mmol), adding 120ml of dichloromethane into the system, adding 40ml of methanol into the system, refluxing for 48 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-114(6.27g, 91% yield) was obtained as a yellow powder.

Weighing the intermediate C-114(5.90g,6mmol), adding the ligand A-114(5.24g,18mmol), adding 120ml of absolute ethanol into the system, refluxing for 36 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-114 (1.66g, 26% yield) was obtained by silica gel column chromatography using dichloromethane and toluene as solvents and concentrating the filtrate to give a solid which was greater than 99% pure by HPLC.

Mass spectrum calculated 1063.17; the test value was 1063.28.

The calculated value of the elemental analysis (%) > is C: 64.39; h is 3.70; f is 5.36; 18.08 parts of Ir; n is 3.95; o is 4.51, and the test value is C is 64.38; h is 3.71; f is 5.34; 18.07 parts of Ir; n is 3.97; o is 4.52.

Example 9

This example provides an iridium complex of formula I-138, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

weighing A-138(14.57g,50mmol), IrC1 of formula A-138 under nitrogen protection system₃·3H₂O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 300m1 ethylene glycol ethyl ether and 100m1 pure water is added, the mixture is refluxed for 30 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridged ligand form B-138(8.24g, 51% yield) was obtained as a yellow powder.

Weighing the intermediate B-138(8.08g,5mmol), adding silver trifluoromethanesulfonate (5.25g,20mmol), adding 160ml of dichloromethane into the system, adding 53ml of methanol, refluxing for 48 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-138(8.76g, 89% yield) was obtained as a yellow powder.

Weighing the intermediate C-138(8.36g,8.5mmol), adding the ligand D-138(9.91g,34mmol), adding 170ml of absolute ethanol into the system, refluxing for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-138 (2.64g, 31% yield) was obtained by silica gel column chromatography using toluene as solvent and concentrating the filtrate to precipitate a solid with an HPLC purity of greater than 99%.

Mass spectrum calculated 1003.14; the test value was 1003.57.

The calculated value of the elemental analysis (%) > is C: 65.85; h is 3.82; f is 3.79; 19.16 parts of Ir; n is 4.19; o is 3.19, and the test value is C is 65.87; h is 3.85; f is 3.79; 19.17 parts of Ir; n is 4.16; o is 3.16.

Example 10

This example provides an iridium complex of formula i-157, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

weighing A-157(10.32g,50mmol), IrC1 of formula A under nitrogen protection₃·3H₂O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 210m1 ethylene glycol ethyl ether and 70m1 pure water is added, the mixture is refluxed for 30 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. Bridged ligand B-157(6.51g, 51% yield) was obtained as a yellow powder.

Weighing the intermediate B-157(5.74g,4.5mmol), adding silver trifluoromethanesulfonate (3.54g,13.5mmol), adding 120ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 36 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-157(6.89g, 94% yield) was obtained as a yellow powder.

Weighing the intermediate C-157(6.51g,8mmol), adding the ligand D-157(6.19g,20mmol), adding 130ml of absolute ethanol into the system, refluxing for 30 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-157 (1.82g, 25% yield) was obtained by silica gel column chromatography using dichloromethane as solvent and concentrating the filtrate to give a solid which was greater than 99% pure by HPLC.

Mass spectrum calculated 911.18; the test value was 911.43.

The calculated value of the elemental analysis (%) > is C: 61.95; h is 6.41; f is 4.17; 21.10 parts of Ir; n is 4.61; o is 1.76, and the test value is C is 61.95; h is 6.41; f is 4.17; 21.10 parts of Ir; n is 4.61; o is 1.76.

Example 11

This example provides an iridium complex of formula I-176, which is prepared by the following reaction scheme:

the specific preparation method comprises the following steps:

formula A-176(17.95g,60mmol), IrC1 was weighed under nitrogen protection₃·3H₂O (7.05g,20mmo1) is put into a reaction system, a mixed solution of 330m1 ethylene glycol ethyl ether and 110m1 purified water is added, the mixture is refluxed for 24 hours under the protection of nitrogen, then the mixture is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridged ligand B-176 was obtained as a yellow powder (6.43g, 39% yield).

Weighing the intermediate B-176(5.77g,3.5mmol), adding silver trifluoromethanesulfonate (1.98g,7.7mmol), adding 120ml of dichloromethane into the system, adding 40ml of methanol, refluxing for 48 hours under the protection of nitrogen, cooling to room temperature, and concentrating the filtrate of column chromatography (short column) until solid is separated out. The iridium complex intermediate of formula C-176(6.58g, 94% yield) was obtained as a dark yellow powder.

Weighing the intermediate C-176(6.00g,6mmol), adding the ligand D-176(7.65g,18mmol), adding 120ml of absolute ethanol into the system, refluxing for 28 hours under the protection of nitrogen, filtering, washing with alcohol, and drying. The final yellow compound of formula I-176 (1.89g, 26% yield) was obtained by silica gel column chromatography using dichloromethane and toluene as solvents and concentrating the filtrate to give a solid which was greater than 99% pure by HPLC.

Mass spectrum calculated 1212.62; the test value was 1212.90.

The calculated value of the elemental analysis (%) is 38.63; f, 40.73; 15.85 parts of Ir; n is 3.47; o is 1.32, and the test value is C is 38.62; f, 40.71; 15.83 parts of Ir; n is 3.49; o is 1.35.

The synthesis methods of other iridium complexes are the same as those described above, and are not repeated here, and the mass spectrum or molecular formula of other synthesis embodiments is shown in table 1 below:

TABLE 1

Compound (I)	Molecular formula	Calculated mass spectrum	Calculated mass spectrum
				Formula I-1	C39H21D4F2IrN2O4	819.88	819.50
Formula I-24	C43H23F12IrN2O4	1051.86	1051.42
				Formula I-35	C61H51F4IrN2O4	1144.30	1144.07
Formula I-55	C63H67D2F2IrN2O4	1150.48	1150.76
				Formula I-79	C39H6D2F19IrN2O4	1123.70	1123.24
Formula I-107	C50H32F2IrN3O	921.04	921.62
				Formula I-121	C75H44F4IrN3O2	1287.41	1287.18
Formula I-130	C57H33F9IrN3O3	1171.11	1171.64
				Formula I-146	C58H35D9F2IrN3O2	1054.28	1054.60
Formula I-166	C49H31F13IrN3O	1117.00	1117.49

The embodiment of the invention also provides an organic electroluminescent device prepared by using the iridium complex provided by the embodiment, and specifically, the organic electroluminescent device is an organic electroluminescent device, wherein the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode.

The organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer, and a composite layer of electron injection technical layers, and at least one layer may or may not include the iridium complex.

Specifically, the light-emitting layer includes a host material and a dopant material; wherein, the host material can be 4,4'-N, N' -biphenyl dicarbazole (CBP), but is not limited thereto; the doping material can be the iridium complex.

In practical applications, the method for manufacturing the organic electroluminescent device can refer to device example 1 below.

Device example 1

Embodiment 1 of the device provides a red phosphorescent organic electroluminescent device, and the preparation method comprises the following steps:

coating with a thickness ofThe ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, and the substrate was washed for 5 minutes and sent to an evaporation coater. Under vacuum conditions, the standard pressure was set at 1X 10^-6And (4) supporting. Thereafter, the ITO substrate was coated with CuPc CBP + Iridium Complex represented by formula I-1 (5%)And the sequence of (a) and (b) forming layers of organic material.

Referring to the above-mentioned method, the iridium complexes represented by the formula I-1 were replaced with iridium complexes represented by the formulae I-2, I-11, I-24, I-35, I-44, I-55, I-62, I-79, I-83, and I-96, respectively, to prepare organic electroluminescent devices of the corresponding compounds.

Comparative device example 1

An organic electroluminescent device was fabricated in accordance with the method provided in device example 1, except that the doping material of the light-emitting layer (the iridium complex represented by formula I-1) was replaced with (btp)₂Ir(acac)。

Among them, the compounds used in the embodiments of the present invention are copper (II) phthalocyanine (CuPc), NPB, (btp)₂Ir(acac)，Alq₃And the structural formula of CBP is as follows:

the organic electroluminescent device prepared as above was subjected to the driving voltage, current efficiency and service life (T95) tests, and the results are shown in table 2.

TABLE 2

Doping material for device	Drive voltage (V)	Current (mA)	Current efficiency (cd/A)	T95(h)
					(btp)2Ir(acac)	8.1	9	16.9	560
Formula I-1	3.4	9	35.7	1070
					Formula I-2	3.2	9	36.4	1050
Formula I-11	3.7	9	39.1	1030
					Formula I-24	3.1	9	34.2	1040
Formula I-35	3.3	9	37.2	990
					Formula I-44	3.4	9	36.1	1060
Formula I-55	3.8	9	35.1	1040
					Formula I-62	3.0	9	35.7	1100
Formula I-79	3.5	9	35.6	1060
					Formula I-83	3.2	9	39.5	1070
Formula I-96	3.6	9	34.6	1040

As can be seen from table 1, compared with the existing doped material, under the same current condition, the iridium complex provided by the embodiment of the invention has a lower driving voltage, and the current efficiency and the service life are obviously higher.

Device example 2

Embodiment 2 of the device provides a green phosphorescent organic electroluminescent device, and the preparation method comprises the following steps:

coating with a thickness ofThe ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, and the substrate was washed for 5 minutes and sent to an evaporation coater. Firstly, evaporating N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine ('2-TNATA') 60nm on an ITO (anode), then evaporating NPB 60nm, a host substance 4,4'-N, N' -biphenyl dicarbazole ('CBP') and a doping material (an iridium complex shown in a formula I-100) according to a weight ratio of 90:10, mixing and evaporating 30nm, evaporating a hole blocking layer ('BALq') 10 nm), evaporating an electron transport layer ('Alq 3') 40nm, evaporating an electron injection layer LiF 0.2nm, and evaporating cathode Al 150nm to prepare the organic electroluminescent device. The performance luminescence characteristics of the obtained device are tested by adopting a KEITHLEY 2400 type source measuring unit and a CS-2000 spectral radiance luminance meter to evaluate the driving voltage, the service life and the luminescence efficiency.

Referring to the above-mentioned method, the iridium complexes represented by the formulae I-100 are replaced with iridium complexes represented by the formulae I-107, I-114, I-121, I-130, I-138, I-146, I-157, I-166, and I-176, respectively, to prepare organic electroluminescent devices of the corresponding compounds.

Comparative device example 2

An organic electroluminescent device was fabricated by the method provided in device example 2, except that the doping material (iridium complex represented by formula I-100) of the light-emitting layer was replaced with Ir (ppy)₃. Wherein, Ir (ppy)₃The structural formula of (A) is as follows:

the organic electroluminescent device prepared as above was examined for driving voltage, luminous efficiency and service life (T95), and the results are shown in table 3.

TABLE 3

Doping material for device	Drive voltage (V)	Luminance (cd/cm)2)	Efficiency (cd/A)	T95(h)
					Ir(ppy)3	6.0	5000	23.0	56.1
Formula I-100	3.1	5000	83.4	780
					Formula I-107	3.3	5000	86.8	761
Formula I-114	3.4	5000	87.5	792
					Formula I-121	3.8	5000	85.6	801
Formula I-130	4.0	5000	88.1	826
					Formula I-138	3.5	5000	79.9	751
Formula I-146	3.7	5000	84.2	781
					Formula I-157	3.9	5000	90.0	792
Formula I-166	3.8	5000	86.5	738
					Formula I-176	3.2	5000	81.9	827

As can be seen from Table 2, the organic electroluminescent device prepared by using the iridium complex provided by the embodiment of the invention as the doping material of the light-emitting layer and the conventional iridium complex Ir (ppy)₃Compared with the organic electroluminescent device prepared by the doped material of the luminescent layer, the driving voltage is obviously reduced, and the luminous efficiency and the service life are obviously improved.

Another object of an embodiment of the present invention is to provide a display apparatus, including a functional module and a display module, where the display module includes the above organic electroluminescent device. Specifically, the display device may be a mobile phone, a notebook computer, a tablet computer, and the like, but is not limited thereto.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.