CN108164564A - A kind of metal iridium complex and the organic electroluminescence device comprising the metal iridium complex - Google Patents

Abstract

The invention discloses a metal iridium complex and an organic electroluminescent device comprising the metal iridium complex. The general structural formula of the metal iridium complex is shown in Formula I. The electroluminescence of the metal iridium complex proposed by the invention is green to red, has high luminous efficiency, and at the same time, the material has good thermal stability, and the material is easy to prepare and purify, so it is an ideal choice as a luminescent material for an organic electroluminescent device.

Description

A metal iridium complex and organic electroluminescence comprising the metal iridium complex device

technical field

The invention relates to the technical field of organic electroluminescent diodes. More specifically, it relates to a metal iridium complex and an organic electroluminescent device comprising the metal iridium complex.

Background technique

Organic electroluminescence (referred to as OLED) and related research As early as 1963, pope et al. first discovered the electroluminescence phenomenon of organic compound single crystal anthracene. In 1987, Kodak Corporation of the United States made an amorphous film device by evaporating organic small molecules, which reduced the driving voltage to less than 20V. This type of device is ultra-thin, fully cured, self-illuminating, high brightness, wide viewing angle, fast response speed, low driving voltage, low power consumption, bright color, high contrast, simple process, good temperature characteristics, and can realize flexible display. And other advantages, can be widely used in flat panel displays and surface light sources, so it has been widely researched, developed and used.

Organic electroluminescent materials are divided into two categories: organic electroluminescent materials and organic electrophosphorescent materials. Among them, organic electroluminescence is the result of radiation inactivation of singlet excitons. During the light emission process, triplet excitons and singlet excitons are generated simultaneously. Usually the ratio of singlet excitons to triplet excitons is 1:3, and according to the prohibition effect of quantum statistics, triplet excitons mainly undergo non-radiative attenuation, which contributes very little to luminescence, and only singlet excitons Therefore, for organic/polymer electroluminescence devices, the fundamental reason why the luminous efficiency is difficult to improve is that the luminescence process is the luminescence of singlet excitons.

In the early stage of organic light-emitting device research, people put forward the idea of triplet light emission. Forrest's group used octaethylporphyrin platinum doped in the small molecule host material octahydroxyquinoline aluminum to make a red electroluminescent phosphorescent light-emitting device. The external quantum efficiency reached 4%. So far, the research on electrophosphorescence has attracted great attention from the academic circle, and the research on organic electrophosphorescence has developed rapidly in the following years. Among them, the iridium complex is a kind of phosphorescent material that has been developed most and has the best application prospect because of its short triplet lifetime and good luminescent properties. Because phosphorescent materials have strong triplet state quenching in solids, generally Both use iridium complexes as doped guest materials, and materials with wider band gaps as doped host materials, and obtain high luminous efficiency by energy transfer or directly trapping excitons on the guest to emit light.

Organic electroluminescent green phosphorescent materials are the earliest studied and the most mature class of materials. In 2004, Hino et al. produced a phosphorescent device by spin coating, with a maximum external quantum efficiency of 29cd/A. The high efficiency achieved by this simple device structure can be attributed to the good film formation of the material and the energy transfer from the host to the guest material. . Adachi et al. doped (ppy)2Ir(acac) into TAZ and used HMTPD as the hole transport layer to obtain a green light device with a maximum external quantum efficiency of 20% and an energy efficiency of 65lm/W. After calculation, the internal The quantum efficiency is almost 100%, and both triplet and singlet excitons are utilized simultaneously.

From the perspective of luminous color, compared with phosphorescent materials of other colors, the development of blue photophosphorescent materials is not only the latest start, but also the least ideal. It is still a very challenging subject. Mechanism studies have shown that as the energy level of the triplet state increases, not only the rate of radiative transitions increases, but also the rate of non-radiative transitions increases, and the increase of the latter is often more obvious, and the overall effect makes the luminescence The efficiency drops, which makes it difficult to realize the blue shift of the luminous wavelength and high efficiency in the research of blue light materials at the same time, and often favor one over the other. Therefore, no blue phosphorescent material with superior comprehensive performance has been reported so far.

Contents of the invention

In order to solve the above technical problems, the present invention provides a metal iridium complex with green to red light emission and high luminous efficiency and an organic electroluminescence device comprising the metal iridium complex.

The present invention specifically provides a metal iridium complex shown in formula I:

in:

R ₁ and R ₂ each independently represent C1-C10 alkyl, C4-C10 cycloalkyl, deuterium-substituted C1-C10 alkyl, deuterium-substituted C4-C10 cycloalkyl, C1-C8 alkane Oxygen, deuterium-substituted C1-C8 alkoxy, C1-C8 alkylthio, deuterium-substituted C1-C8 alkylthio, fluorine or cyano;

R ₃ , R ₄ , and R ₅ each independently represent hydrogen, deuterium hydrogen, fluorine, C1-C8 alkyl, deuterium-substituted C1-C8 alkyl, C1-C8 alkoxy, deuterium-substituted C1-C8 Alkoxy, C1-C8 silyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, substituted or unsubstituted C ₆ -C ₂₀ aryloxy, substituted or unsubstituted C ₆ - C ₂₀ arylthio, fluorine or cyano;

The substituents described in the substituted C ₆ -C ₂₀ aryl, substituted C ₆ -C ₂₀ aryloxy and substituted C ₆ -C ₂₀ arylthio are each independently selected from hydrogen, deuterium hydrogen, halogen atom, hydroxyl, cyano, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy, C ₃ -C ₂₀ cycloalkane or C One or more of ₃ -C ₂₀ cycloalkene groups;

A means C or N;

X represents O, S or Se;

n represents 1, 2 or 3 each independently.

Preferably, the structural formula of the compound of formula I is specifically shown as II and III, but not limited to the structures listed below:

in,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X and n are the same as R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X and n in formula I, respectively.

Further preferably, the structural formula of the compound of formula II is specifically the structures shown in the following formulas II-01 to II-54, but not limited to the structures listed below:

Further preferably, the structural formula of the compound of formula III is specifically the structures shown in the following formulas III-01 to III-51, but not limited to the structures listed below:

The present invention also provides an organic electroluminescence device, which comprises a substrate, an anode layer disposed on the substrate, a hole transport layer disposed on the anode layer, an organic electroluminescence layer disposed on the hole transport layer A light-emitting layer, an electron transport layer disposed on the organic light-emitting layer, and a cathode layer disposed on the electron-transport layer; wherein, the material of the organic light-emitting layer includes one or more of the above-mentioned metal complexes.

Preferably, a hole injection layer is further provided between the anode layer and the hole transport layer in the organic electroluminescent device.

Wherein, the substrate can be glass or a flexible substrate, and the flexible substrate is made of a material among polyester and polyimide compounds;

Preferably, the anode layer can be made of inorganic materials or organic conductive polymers, and the inorganic materials are metal oxides such as indium tin oxide (referred to as ITO), zinc oxide, tin zinc oxide, or metals with higher functional functions such as gold, silver, and copper, The optimal choice is ITO, and the organic conductive polymer is preferably a material in polythiophene/sodium polyvinylbenzenesulfonate (PEDOT:PSS) and polyaniline;

Preferably, the cathode layer generally uses metals with lower functional functions such as lithium, magnesium, silver, calcium, strontium, aluminum, indium, or their alloys with copper, gold, and silver, or electrode layers formed alternately between metals and metal fluorides, The present invention is preferably a magnesium/silver alloy layer;

Preferably, both the hole transport layer and the hole injection layer can use triarylamine materials, preferably NPB or DNTPD, and the structural formula is as follows:

Preferably, the electron transport layer is generally a metal-organic complex, preferably Alq3, Liq, BPhen, etc., and the structural formula is as follows:

Preferably, the organic light-emitting layer can generally use small molecule materials, which can be doped with fluorescent materials or phosphorescent dyes. The material of the organic light-emitting layer of the present invention includes the metal complex proposed by the present invention, and the metal complex can be used as a phosphorescent doping material. The material emits light in the corresponding host material, and the preferred host material is selected from one or more of the following compounds:

Preferably, the preparation method of the organic electroluminescent device comprises the following steps:

1) Use cleaning agent, deionized water and organic solvent to clean the glass substrate with ITO in several steps;

2) Evaporating a hole injection layer comprising the material of the present invention by vacuum evaporation;

3) Evaporating the hole transport layer of the device by vacuum evaporation;

4) continue to vapor-deposit the light-emitting layer comprising the material of the present invention;

5) continue to evaporate the electron transport layer comprising the material of the present invention;

6) Prepare a metal cathode by vapor deposition, sputtering or spin coating.

Preferably, the hole injection layer has a thickness of 30-50 nm, more preferably the hole injection layer has a thickness of 40 nm,

Preferably, the hole transport layer has a thickness of 5-15 nm, more preferably the hole transport layer has a thickness of 10 nm.

Preferably, the thickness of the organic light-emitting layer is 10-100 nm, and more preferably, the thickness of the organic light-emitting layer is 50 nm.

Preferably, the electron transport layer has a thickness of 10-30 nm, and more preferably, the electron transport layer has a thickness of 20 nm.

Preferably, the cathode layer has a thickness of 90-110 nm, and more preferably the cathode layer has a thickness of 100 nm.

The present invention also provides an organic electroluminescent material, wherein the raw material of the organic electroluminescent material includes one or more of the above-mentioned metal complexes.

The present invention also provides the application of the above-mentioned metal complex in the preparation of organic electroluminescent devices.

The present invention also provides the application of the above-mentioned metal complex in the preparation of organic electroluminescent materials.

The application of the metal complex of the present invention as a luminescent material alone or as a host material or a dopant material in a luminescent layer is also within the scope of protection.

Unless otherwise specified, the raw materials used in the present invention can be commercially available, and any range described in the present invention includes the end value and any numerical value between the end value and the end value or any numerical value between the end value. any subrange of .

The beneficial effects of the present invention are as follows:

The metal iridium complex proposed by the present invention is a series of pyridine metal complex electrophosphorescent materials with a benzoheterocyclic structure. A series of phosphorescent materials prepared by the modification of bases; the electroluminescence of the metal complexes involved in the present invention is green to red, with high luminous efficiency, and at the same time, the thermal stability of the material is good, and the material is easy to prepare and easy to sublimate and purify, and has a very wide range of applications. market prospects.

Description of drawings

FIG. 1 is a schematic diagram of the structure of an OLED device in Embodiment 10 of the present invention.

Detailed ways

In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and accompanying drawings. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

The specific implementation manners of the present invention will be further described in detail below in conjunction with the accompanying drawings.

FIG. 1 is a schematic diagram of the structure of an OLED device in Embodiment 10 of the present invention. Among them, 1-substrate, 2-anode layer, 3-hole injection layer, 4-hole transport layer, 5 organic light-emitting layer, 6-electron transport layer, 7-cathode layer.

In the present invention, the preparation methods are conventional methods unless otherwise specified. The raw materials used can be obtained from open commercial channels unless otherwise specified, and the percentages are all mass percentages unless otherwise specified. A series of novel metal complexes provided by the present invention, all reactions are carried out under well-known suitable conditions, some relate to simple organic preparation, for example, the preparation of phenylboronic acid derivatives can be synthesized by skilled operation skills, in this The invention is not described in detail.

The synthetic route of the compound shown in the structural formula I of the present invention and the compound of the formula II is shown below, and those skilled in the art should understand that similar routes can also be used for the synthesis of other compounds.

The synthetic route of the compound shown in the structural formula I of the present invention and the compound of the formula III is shown below, and those skilled in the art should understand that similar routes can also be used for the synthesis of other compounds.

The above reaction scheme exemplifies the synthesis route of the general formula I of the compound structure, and prepared key intermediates Int-1, Int-2, and Int-3 compounds. Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X and n are the same as defined above;

The following abbreviations are used in the examples of the present invention:

Table 1 Abbreviations and full names

abbreviation full name THF Tetrahydrofuran n-BuLi n-Lithium DCM Dichloromethane (PinB) ₂ pinacol diboronate Pd(PPh ₃ ) ₄ Tetrakis(triphenylphosphine)palladium DAST Diethylaminosulfur trifluoride

Example 1

The preparation of compound II-05, the structural formula is as follows:

The preparation method of above-mentioned compound II-05, comprises the steps:

The first step: the preparation of compound 3-bromo-2-hydroxybenzaldehyde

Disperse 14.5g of anhydrous magnesium chloride in 250ml of anhydrous tetrahydrofuran, add 7.5g of paraformaldehyde and 21ml of triethylamine, stir and react for 30 minutes, add 17.5g of o-bromophenol, after the addition, stir and raise the temperature to reflux reaction After 16 hours, cool to room temperature, add 500ml of dilute hydrochloric acid, extract with ethyl acetate, dry the organic phase with anhydrous sodium sulfate, filter, concentrate under reduced pressure to dryness, separate and purify with silica gel column to obtain 30g of yellow oil.

The second step: the preparation of compound 7-bromo-2-nitrobenzofuran

Take 20g of the oil obtained in the first step and dissolve it with 250ml of acetone. Under the protection of nitrogen, add 28g of anhydrous potassium carbonate, cool to 10°C with an ice-water bath, add 28g of bromonitromethane, keep stirring for 2 hours, filter, The filtrate was concentrated to dryness under reduced pressure, 10 ml of concentrated hydrochloric acid and 200 ml of methanol were added, the temperature was raised to reflux for 30 minutes, cooled to room temperature, filtered, and the filter cake was washed with methanol to obtain 18.5 g of a yellow solid.

The third step: the preparation of compound 7-bromo-2-aminobenzofuran

Take 18g of the second step product 7-bromo-2-nitrobenzofuran and dissolve it with 100ml of ethanol and 100ml of tetrahydrofuran, add 10ml of water and 36g of ammonium chloride, add 20g of iron powder under stirring at room temperature, and stir React for 16 hours, filter, and concentrate the filtrate to dryness under reduced pressure. The residue can be purified by acid-base method to obtain 11 g of yellow solid.

Step 4: Preparation of Compound Int.-1

Add 600ml of glacial acetic acid and 20ml of water to the reaction flask, raise the temperature to reflux, slowly add 10g of 7-bromo-2-aminobenzofuran and 18.2g of trifluoroacetylacetone dropwise under stirring and dissolve in 100ml of dry DMF solution , After dropping, reflux reaction for 3 hours, cooled to room temperature, concentrated under reduced pressure to dryness, separated and purified with silica gel column to obtain 13g of Int-1 as a white solid.

Step 5: Preparation of compound Int-2

Mix 10.0g of compound Int-1 obtained in the fourth step with 8.5g of triisopropyl borate and 200ml of dry tetrahydrofuran. Under the protection of nitrogen, cool the temperature to -78°C with liquid nitrogen, and slowly add 14.5ml of 2.5M n-Butyllithium-hexane solution, heat preservation reaction for 1 hour, rise to room temperature and stir for 30 minutes, add 100 ml of dilute hydrochloric acid dropwise and stir for 30 minutes, separate the organic phase, extract the aqueous phase with ethyl acetate, and dry the organic phase. After filtration, the filtrate was concentrated to dryness under reduced pressure. The residue was dispersed with petroleum ether and filtered to obtain 7.3 g of Int-2 as a white solid.

Step 6: Preparation of Compound Int-3

The 5.5g intermediate Int-2 obtained in the fifth step and the 2-bromopyridine of 4.4g, the anhydrous sodium carbonate of 8.0g, the ethanol of 50ml toluene and 20ml and the water of 20ml are mixed, then add the catalyst Pd of 40mg (PPh3 ) 4, under the protection of nitrogen, heat up and reflux for 12 hours, cool to room temperature, separate the organic phase, extract the aqueous phase with ethyl acetate, dry the organic phase, filter, concentrate the filtrate to dryness under reduced pressure, and separate and purify the residue with a silica gel column , to obtain 5.0 g of Int-3 as a yellow solid.

Step 7: Preparation of Compound II-05

5.0g of the sixth step compound Int-3 and 3.6g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and stirred for 24 hours, then cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 2.7 g of compound II-05, a yellow solid, TOF-MS: m/z (%) = 829.1676 [M ⁺ +1], confirmed compound II-05 correct.

Example 2

The preparation of compound II-23, structural formula is as follows:

For the preparation of the above-mentioned compound II-23, the intermediate Int.-4 was prepared according to the preparation method of the first step to the sixth step in Example 1, and the preparation method of other compounds comprises the following steps:

The first step: preparation of compound Int.-5

6.0g of intermediate Int.-4 was dispersed in 150ml of deuterated ethanol, 2.5g of sodium ethoxide solid was added, stirred and heated to reflux for 3 days, cooled to room temperature, concentrated to dryness under reduced pressure, added 150ml of ice water and 150ml of Ethyl acetate, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, dried, filtered, the filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column, and 5.0 g of white solid was obtained.

The second step: the preparation of compound II-23

5.0g of the first step compound Int.-5 and 3.4g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 2.0 g of compound II-23, a yellow solid, TOF-MS: m/z (%) = 841.3182 [M ⁺ +1], confirmed that compound II-23 23 is correct.

Example 3

The preparation of compound II-26, structural formula is as follows:

For the preparation of the above-mentioned compound II-26, the intermediate Int.-6 was prepared according to the preparation method of the first step to the sixth step in Example 1, and the preparation method of other compounds comprises the following steps:

The first step: preparation of compound Int.-7

10.0g of intermediate Int.-6 was dispersed in 150ml of deuterated ethanol, 3.5g of sodium ethoxide solid was added, stirred and heated to reflux for 5 days, cooled to room temperature, concentrated to dryness under reduced pressure, added 150ml of ice water and 150ml of Ethyl acetate, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, dried, filtered, the filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column, and 7.5 g of white solid was obtained.

The second step: the preparation of compound II-26

5.0g of the first step compound Int.-7 and 2.7g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 2.4 g of compound II-26, a yellow solid, TOF-MS: m/z (%) = 933.4588 [M ⁺ +1], confirmed that compound II-26 26 correct.

Example 4

The preparation of compound II-51, structural formula is as follows:

The preparation method of above-mentioned compound II-51, comprises the steps:

The first step: preparation of compound Int.-8

Add 300ml of glacial acetic acid and 10ml of water to the reaction flask, raise the temperature to reflux, slowly add 5.0g of 7-bromo-2-aminobenzofuran and 11.0g of 2-tetrahydrofuroylacetone dropwise under stirring, dissolve in 50ml of dry DMF solution, after dropping, reflux reaction for 3 hours, cooled to room temperature, concentrated to dryness under reduced pressure, separated and purified with silica gel column to obtain 7.5 g of Int.-8 as a white solid.

The second step: the preparation of compound Int.-9

Dissolve 7.0g of compound Int.-8 obtained in the first step in 120ml of dry tetrahydrofuran, under the protection of nitrogen, cool the temperature to -78°C with liquid nitrogen, and slowly add 10ml of 2.5M n-butyllithium-hexane solution dropwise , keep warm for 30 minutes, add 6.0g of triisopropyl borate dropwise, rise to room temperature and stir for 1 hour, add 100ml of dilute hydrochloric acid dropwise and stir for 30 minutes, separate the organic phase, and extract the aqueous phase with ethyl acetate. The phase was dried and filtered, and the filtrate was concentrated to dryness under reduced pressure. The residue was dispersed with petroleum ether and filtered to obtain 4.5 g of Int.-9 as a white solid.

The third step: preparation of compound Int.-10

For the preparation method of compound Int.-10, please refer to the sixth step of Example 1, and replace the intermediate Int.-2 in the sixth step of Example 1 with the product Int.-9 in the second step of this example to prepare Compound formula Int.-10, white solid.

The fourth step: the preparation of compound II-51

5.0g of the third step compound Int.-10 and 3.6g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 3.5 g of compound II-51, a yellow solid, TOF-MS: m/z (%) = 831.2217 [M ⁺ +1], confirmed that compound II-51 51 correct.

Example 5

The preparation of compound II-52, the structural formula is as follows:

For the preparation of the above-mentioned compound II-52, the intermediate Int.-10 was prepared according to the preparation method from the first step to the third step in Example 4, and the preparation method of other compounds included the following steps:

The first step: preparation of compound Int.-11

10.0g of intermediate Int.-10 was dispersed in 150ml of deuterated ethanol and 10ml of deuterated tetrahydrofuran, 4.5g of sodium ethoxide solid was added, stirred and heated to reflux for 5 days, cooled to room temperature, concentrated to dryness under reduced pressure, and 150ml of ice water and 150ml of ethyl acetate, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, dried, filtered, the filtrate was concentrated under reduced pressure to dryness, separated and purified by a silica gel column to obtain 9.5 g of a white solid.

The second step: the preparation of compound II-52

5.0g of the first step compound Int.-11 and 3.5g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF, and under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 3.0 g of compound II-52, a yellow solid, TOF-MS: m/z (%) = 840.2845 [M ⁺ ], confirmed that compound II-52 was correct .

Example 6

The preparation of compound III-01, the structural formula is as follows:

The preparation method of above-mentioned compound III-01, comprises the steps:

The first step: preparation of compound Int.-12

10.0g of compound SM-20 (prepared with reference to the method of literature Chemistry-A European Journal, 2016,22(30), P10415) was dispersed in 250ml of ethanol, and 4.5g of acetamidine hydrochloride and 10.0g of potassium hydroxide were added, Stir and heat up to reflux for 2 hours, cool to room temperature, concentrate to dryness under reduced pressure, add 150 ml of ice water, filter, wash the filter cake with water, dry, and separate and purify with a silica gel column to obtain 7.3 g of a yellow solid.

The second step: the preparation of compound Int.-13

For the preparation method of compound Int.-13, please refer to the second step of Example 4, replace the intermediate Int.-8 in the second step of Example 4 with the product Int.-12 in the first step in this example, and prepare Compound formula Int.-13, white solid.

The third step: preparation of compound Int.-14

For the preparation method of compound Int.-14, please refer to the third step of Example 4, and replace the intermediate Int.-9 in the third step of Example 4 with the product Int.-13 in the second step of this example to prepare Compound formula Int.-14, yellow solid.

Step 4: Preparation of compound III-01

5.0g of the third step compound Int.-14 and 4.3g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 3.7 g of compound III-01, a yellow solid, TOF-MS: m/z (%) = 776.1918 [M ⁺ +1], confirmed that compound III-01 01 is correct.

Example 7

The preparation of compound III-18, structural formula is as follows:

The first step: preparation of compound Int.-15

10.0g of compound SM-30 (prepared with reference to the method of literature Chemistry-A European Journal, 2016,22(30), P10415) was dispersed in 250ml of ethanol, and 4.9g of isopropylformamidine hydrochloride and 8.8g of hydrogen were added Potassium oxide, stirred and heated to reflux for 2 hours, cooled to room temperature, concentrated to dryness under reduced pressure, added 150ml of ice water, filtered, washed the filter cake with water, dried, separated and purified by silica gel column to obtain 8.2g of yellow solid.

The second step: the preparation of compound Int.-16

For the preparation method of compound Int.-16, please refer to the second step of Example 4, and replace the intermediate Int.-8 in the second step of Example 4 with the product Int.-15 in the first step in this example to prepare Compound formula Int.-16, yellow solid.

The third step: preparation of compound Int.-17

For the preparation method of compound Int.-17, please refer to the third step of Example 4, and replace the intermediate Int.-9 in the third step of Example 4 with the product Int.-16 in the second step of this example to prepare Compound formula Int.-17, yellow solid.

The fourth step: the preparation of compound III-18

5.0g of the third-step compound Int.-16 and 3.3g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 2.5 g of compound III-18, a yellow solid, TOF-MS: m/z (%) = 858.2692 [M ⁺ +1], confirmed that compound III-18 18 is correct.

Example 8

The preparation of compound III-12, structural formula is as follows:

The preparation method of above-mentioned compound III-12, comprises the steps:

The first step: preparation of compound Int-18

10.0 g of compound SM-20 and 100 g of urea were mixed, stirred and heated to reflux, stirred and reacted for 2 hours, cooled to 100 ° C, added dropwise with 10% aqueous sodium hydroxide solution, stirred to room temperature, then added dropwise with dilute hydrochloric acid for neutralization, Filter, wash with water, dry, and recrystallize with ethanol to obtain 8.2 g of compound Int-18 as a white solid.

The second step: the preparation of compound Int-19

Mix 8.0g of compound Int-18 and 48ml of DAST, under the protection of nitrogen, raise the temperature to 40°C and stir for 24 hours, cool to room temperature, concentrate to dryness under reduced pressure, add 100ml of ice water, filter, wash the filter cake with water, vacuum After drying, separation and purification with a silica gel column, 7.6 g of compound Int-19 was obtained as a yellow solid.

The third step: preparation of compound Int.-20

For the preparation method of compound Int.-20, please refer to the fifth step in Example 1, and replace the intermediate Int.-1 in the fifth step of Example 1 with the product Int.-19 in the second step in this example to prepare Compound formula Int.-20, yellow solid.

Step 4: Preparation of Compound Int.-21

For the preparation method of compound Int.-21, please refer to the third step of Example 4, and replace the intermediate Int.-9 in the third step of Example 4 with the product Int.-20 in the third step in this example to prepare Compound formula Int.-21, yellow solid.

Step 5: Preparation of Compound III-12

5.0g of the fourth step compound Int.-21 and 4.2g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 3.3 g of compound III-12, a yellow solid, TOF-MS: m/z (%) = 780.1665 [M ⁺ +1], confirmed that compound III-12 12 is correct.

Example 9

The preparation of compound III-39, structural formula is as follows:

For the preparation of the above-mentioned compound III-39, the intermediate Int.-22 was prepared according to the preparation method from the first step to the third step in Example 6, and the preparation method of other compounds included the following steps:

The first step: preparation of compound Int.-23

10.0g of intermediate Int.-22 was dispersed in 150ml of deuterated ethanol, 4.0g of sodium ethoxide solid was added, stirred and heated to reflux for 5 days, cooled to room temperature, concentrated to dryness under reduced pressure, added 150ml of ice water and 150ml of Ethyl acetate, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, dried, filtered, the filtrate was concentrated to dryness under reduced pressure, separated and purified by silica gel column to obtain 10.0 g of a yellow solid.

The second step: the preparation of compound III-39

5.0g of the first step compound Int.-23 and 3.3g of iridium chelate SM-10 were dispersed in 120ml of ethylene glycol ether and 120ml of dry DMF. Under the protection of nitrogen, the temperature was raised to 135°C and the reaction was stirred for 24 hours. Cooled to room temperature, concentrated under reduced pressure to remove the solvent, separated and purified on a silica gel column to obtain 2.1 g of compound III-39, a yellow solid, TOF-MS: m/z (%) = 858.3406 [M ⁺ +1], confirmed that compound III-39 39 correct.

Example 10

An OLED device, as shown in Figure 1, comprises a substrate 1, an anode layer 2 arranged on the substrate 1, a hole injection layer 3 arranged on the anode layer 2, a hole transport layer arranged on the hole injection layer 3 layer 4 , an organic light-emitting layer 5 disposed on the hole-transport layer 4 , an electron-transport layer 6 disposed on the organic light-emitting layer 5 , and a cathode layer 7 disposed on the electron-transport layer 6 .

The preparation method of above-mentioned OLED device comprises the following steps:

1) The glass substrate coated with the ITO conductive layer is ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonicated in acetone/ethanol mixed solvent for 30 minutes, and baked in a clean environment until completely dry, Irradiate with a UV light cleaner for 10 minutes and bombard the surface with a low-energy positive ion beam.

2) Place the above-mentioned treated ITO glass substrate in a vacuum chamber, evacuate to 1×10 ^-5 ~ 9×10 ^-3 Pa, and continue to vapor-deposit the compound DNTPD on the above-mentioned anode layer film as a hole injection layer , the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40nm; continue to evaporate NPB on the hole injection layer film as the hole transport layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10nm;

3) On the hole transport layer, continue to vapor-deposit one layer of compound formula I and mCBP of the present invention as the light-emitting layer of the device, wherein mCP is a host material and compound formula I of the present invention is a dopant material, and compound formula I and mCBP The evaporation rate ratio is 1:100, the doping concentration of compound formula I in mCBP is 1%, the total evaporation rate is 0.1nm/s, and the evaporation film thickness is 50nm;

4) Continue to vapor-deposit a layer of Liq material on the above-mentioned holes as the electron transport layer of the device, the plating rate is 0.1nm/s, and the vapor-deposited film thickness is 20nm; finally, successively vapor-deposit magnesium/silver on the above-mentioned electron transport layer The alloy layer is used as the cathode layer of the device, and the evaporation rate of the magnesium/silver alloy layer is 2.0-3.0nm/s, and the evaporation film thickness is 100nm;

Following the same steps as above, only the compound formula I used in step 3) was replaced with compound II-05 to obtain OLED-1 provided by the present invention;

According to the same steps as above, only the compound formula I used in step 3) is replaced with compound II-23 to obtain OLED-2 provided by the present invention;

According to the same steps as above, only the compound formula I used in step 3) was replaced with compound II-26 to obtain OLED-3 provided by the present invention;

Following the same steps as above, only the compound formula I used in step 3) was replaced with compound II-51 to obtain OLED-4 provided by the present invention;

Following the same steps as above, only the compound formula I used in step 3) was replaced with compound II-52 to obtain OLED-5 provided by the present invention;

Following the same steps as above, only the compound formula I used in step 3) was replaced with compound III-01 to obtain OLED-6 provided by the present invention;

Following the same steps as above, only the compound formula I used in step 3) was replaced with compound III-12 to obtain OLED-7 provided by the present invention;

Following the same steps as above, only the compound formula I used in step 3) was replaced with compound III-18 to obtain OLED-8 provided by the present invention;

According to the same steps as above, only the compound formula I used in step 3) was replaced with compound III-39 to obtain OLED-9 provided by the present invention;

The performance testing results of the obtained devices OLED-1 to OLED-9 are shown in Table 2:

Table 2 performance test results

Conclusion: From the analysis of the performance test results, the metal iridium complex of the present invention emits green light, the color purity is better, and the chromaticity coordinates are in the green light region, and its performance exceeds that of the known green light materials, and it has not been tested in the test device. Under the conditions of packaging, the luminous life of the device is also relatively ideal.

Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those of ordinary skill in the art can also make It is impossible to exhaustively list all the implementation modes here, and any obvious changes or changes derived from the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims (10)

1. The metal iridium complex is characterized in that the metal iridium complex is a compound shown as a formula I

Wherein:

R₁and R₂Each independently represents C1-C10 alkyl, C4-C10 cycloalkyl, deuterium substituted C1-C10 alkyl, deuterium substituted C4-C10 cycloalkyl, C1-C8 alkoxy, deuterium substituted C1-Alkoxy of C8, alkylthio of C1-C8, deuterium substituted alkylthio of C1-C8, fluoro or cyano;

R₃、R₄、R₅each independently represents hydrogen, deuterohydrogen, fluorine, C1-C8 alkyl, deuterium substituted C1-C8 alkyl, C1-C8 alkoxy, deuterium substituted C1-C8 alkoxy, C1-C8 silyl, substituted or unsubstituted C1-C8 alkyl₆-C₂₀Aryl, substituted or unsubstituted C₆-C₂₀Aryloxy, substituted or unsubstituted C₆-C₂₀Arylthio, fluoro or cyano;

said substituted C₆-C₂₀Aryl, substituted C₆-C₂₀Aryloxy and substituted C₆-C₂₀The substituents in the arylthio group are each independently selected from hydrogen, deuterohydrogen, halogen atom, hydroxyl, cyano, C₁-C₂₀Alkyl radical, C₂-C₂₀Alkenyl radical, C₂-C₂₀Alkynyl, C₁-C₂₀Alkoxy radical, C₃-C₂₀Cycloalkyl or C₃-C₂₀One or more kinds of cyclic olefin groups;

a represents C or N;

x represents O, S or Se;

each n independently represents 1, 2 or 3.

2. The iridium complex as claimed in claim 1, wherein the compound of formula I is a compound represented by formulae II-01 to II-45 and III-01 to III-51

3. An organic electroluminescent device comprising a substrate, an anode layer, a hole transport layer, an organic light-emitting layer, an electron transport layer and a cathode layer in this order, wherein the material of the organic light-emitting layer comprises one or more metal iridium complexes as claimed in claim 1 or 2.

4. The organic electroluminescent device of claim 3, wherein a hole injection layer is further disposed between the anode layer and the hole transport layer.

5. The organic electroluminescent device according to claim 4, wherein the hole injection layer has a thickness of 30 to 50 nm.

6. The organic electroluminescent device according to claim 4, wherein the hole injection layer has a thickness of 40 nm.

7. The organic electroluminescent device according to claim 3, wherein the hole transport layer has a thickness of 5 to 15 nm; the thickness of the organic light-emitting layer is 10-100 nm; the thickness of the electron transmission layer is 10-30 nm; the thickness of the cathode layer is 90-110 nm.

8. The organic electroluminescent device according to claim 3, wherein the hole transport layer has a thickness of 10 nm; the thickness of the organic light-emitting layer is 50 nm; the thickness of the electron transport layer is 20 nm; the thickness of the cathode layer is 100 nm.

9. An organic electroluminescent material, characterized in that a raw material of the organic electroluminescent material comprises one or more of the metal iridium complexes described in claim 1 or 2.

10. Use of the iridium metal complex according to claim 1 or 2 for the preparation of organic electroluminescent devices or organic electroluminescent materials.