CN103936791B - A series of organic electromechanical phosphorescent materials - Google Patents

Abstract

The invention discloses a series of organic electrophosphorescent materials. The general structural formula of the organic electrophosphorescent material is shown in Formula I. The complex electroluminescent material is mainly composed of 4,5-disubstituted phenanthrene and 4,5-disubstituted 9,10-dihydrophenanthrene. Due to the influence of two large sterically hindered electron-donating groups at the 4,5-position and the immobilization of the phenanthrene and 9,10-dihydrophenanthrene hydrocarbon chains, the ability to capture excitons is greatly improved and the phosphorescence is effectively shortened. lifespan, improve luminous efficiency, and improve the performance of light-emitting devices. The compound involved in the present invention has the characteristics of excellent film-forming properties and high luminous efficiency.

Description

A series of organic electrophosphorescent materials

technical field

The invention belongs to the technical field of organic electroluminescence display and relates to a series of organic electroluminescent materials.

Background technique

For 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 generation ratio of singlet excitons and triplet excitons is 1:3, and according to the forbidden effect of quantum prohibition, triplet excitons mainly undergo non-radiative attenuation, which contributes very little to luminescence, and only singlet excitons radiate Luminescence, therefore, for organic/polymer electroluminescent devices, the fundamental reason why it is difficult to improve the luminous efficiency 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 community, 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) ₂ Ir(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, its The internal quantum efficiency is almost 100%, and both triplet and singlet excitons are utilized simultaneously.

Contents of the invention

The object of the present invention is to provide a series of organic electrophosphorescent materials.

The organic electrophosphorescent material provided by the present invention has a general structural formula as shown in formula I,

In the formula I, R ₁ , R ₄ and R ₅ are all selected from hydrogen atom, fluorine atom, methoxy group, cyano group, trifluoromethoxy group, C1-C50 aliphatic hydrocarbon group, C1-C50 aromatic group and Any one of C1-C50 fused ring aromatic groups;

R is any one selected from a _hydrogen atom, a fluorine atom, a trifluoromethyl group, a methoxy group, a methyl group and an aliphatic hydrocarbon group of C1-C50;

M is an iridium or platinum atom;

Z is -CH ₂ CH ₂ - or -CH=CH-;

X is 1, 2 or 3;

When X is 1 or ₂ , R is acetylacetonate, acetoacetyl substituted by C1-C50 aliphatic hydrocarbon group, 2-pyridineformyloxy group or 2-pyridineformyloxy group containing substituent; said containing In the 2-pyridineformyloxy group of the substituent, the substituent is selected from any one of a fluorine atom, a C1-C10 alkyl group, a cyano group and a trifluoromethyl group;

When X is 3, R ₆ is selected from 2-(8-R ₅ -6-R ₃ -4,5-2R ₂ -3-R ₁ -7 _- R phenanthrene) pyridyl or 2-(8-R ₅ -6-R ₃ -4,5-2R ₂ -3-R ₁ -7-R ₄ -9,10-dihydrophenanthrene-2-yl)pyridyl, wherein, R ₁ , R ₄ and R ₅ are all Any one selected from hydrogen atom, fluorine atom, methoxyl group, cyano group, trifluoromethoxyl group, C1-C50 aliphatic hydrocarbon group, C1-C50 aromatic group and C1-C50 fused ring aromatic group; R ₂ Any one selected from hydrogen atom, fluorine atom, trifluoromethyl, methoxy, methyl and C1-C50 aliphatic hydrocarbon groups;

Specifically, the compound shown in the formula I is any one of the compounds shown in the formula I-1a, the formula I-1b, the formula I-2a, the formula I-2b and the formula I-3:

The formula I-1a is specifically the compound shown in PHPT-AC-I:

The formula I-2a is specifically the compound shown in PHIR-AC-I:

The formula I-2b is specifically the compound shown in PHIR-PY-I:

The formula I-3 is specifically the compound shown in PHIR-CJH-I:

The formula I-1a, formula I-1b, formula I-2a, formula I-2b, formula I-3, PHIR-AC-I, PHPT-AC-I, PHIR-PY-I and PHIR-CJH-I Among them, the definition of R ₁ to R ₅ is the same as the definition of R ₁ to R ₅ in formula I in claim 1;

The R ₇ are all hydrogen atoms or C1-C50 aliphatic hydrocarbon groups;

The R ₈ are all selected from any one of a hydrogen atom, a fluorine atom, a C1-C10 alkyl group, a cyano group and a trifluoromethyl group;

Wherein, the compound shown in the PHIR-AC-I is more specifically any one of the following compounds:

The compound shown in the PHPT-AC-I is more specifically any one of the following compounds:

The compound shown in the PHIR-PY-I is more specifically any one of the following compounds:

The compound shown in the PHIR-CJH-I is more specifically any one of the following compounds:

In addition, the luminescent material containing the compound represented by formula I provided by the present invention and the application of the compound represented by formula I in the preparation of luminescent material also belong to the protection scope of the present invention. Wherein, the luminescent material is specifically an organic electrophosphorescent luminescent material, more specifically an organic electroorange phosphorescent luminescent material; , 533, 535, 542 or 512-542nm.

The application of the compound represented by formula I provided by the present invention as a light-emitting layer in the preparation of organic electroluminescent devices and the organic electroluminescent device containing the compound represented by formula I as a light-emitting layer also belong to the protection scope of the present invention. Wherein, the organic electroluminescent device is specifically an organic electrophosphorescent light emitting device, more specifically an organic electroluminescent orange phosphorescent luminescent material; the luminescent wavelength of the luminescent material is specifically 460-620nm, specifically 512, 518, 522, 524, 526, 533, 535, 542 or 512-542nm.

Specifically, the organic electroluminescent device is composed of a transparent substrate, an anode, a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer and a cathode layer sequentially from bottom to top;

Wherein, the material constituting the transparent substrate is glass or a flexible substrate;

The material constituting the anode layer is an inorganic material or an organic conductive polymer; wherein the inorganic material is indium tin oxide, zinc oxide, tin zinc oxide, gold, silver or copper; the organic conductive polymer is selected from polythiophene , at least one of sodium polyvinylbenzenesulfonate and polyaniline;

The material constituting the hole injection layer is TDATA;

The structural formula of the TDATA is as follows:

The material constituting the hole transport layer is NPB;

The structural formula of the NPB is as follows:

The material constituting the organic luminescent layer is a compound shown in formula I and a host material;

Wherein, the host material is mCP, CBP, NATZ or

Among them, the structural formulas of mCP, CBP and NATZ are as follows:

The mass of the compound shown in formula I is 1-10% of the mass of the main material, specifically 5%;

The material constituting the electron transport layer is Alq3, Gaq3 or BPhen;

Among them, the structural formulas of Alq3, Gaq3, BPhen and TPBi are as follows:

The material constituting the cathode layer is selected from any one of the following elements or an alloy of any two or fluorides of the following elements: lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold and silver.

Specifically, the thickness of the hole injection layer is 30-50 nm, specifically 40 nm;

The thickness of the hole transport layer is 5-15nm, specifically 10nm;

The thickness of the organic light-emitting layer is 10-100nm, specifically 50nm;

The thickness of the electron transport layer is 10-30nm, specifically 20nm;

The thickness of the cathode layer is 90-110 nm, specifically 100 nm.

The complex electrophosphorescent material with phenanthrene and 9,10-dihydrophenanthrene structure provided by the present invention is based on 4,5-disubstituted phenanthrene and 4,5-disubstituted 9,10-dihydrophenanthrene main body. Due to the influence of the two large sterically hindered electron-donating groups at the 4,5-position and the immobilization of the phenanthrene and 9,10-dihydrophenanthrene hydrocarbon chains, the ability to capture excitons is greatly improved and the phosphorescence is effectively shortened. lifespan, improve luminous efficiency, and improve the performance of light-emitting devices. The compound involved in the present invention has the characteristics of excellent film-forming properties and high luminous efficiency.

detailed description

The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The raw materials can be obtained from open commercial channels unless otherwise specified.

The compound shown in the formula I provided by the present invention can be prepared according to the following reaction formula:

The testing apparatus and method that following embodiment carries out performance test to OLED material and device are as follows:

OLED device performance testing conditions:

Luminance and chromaticity coordinates: Tested using spectral scanner PhotoResearch PR-715;

Current density and lighting voltage: Tested with Keithley2420 digital source meter;

Power Efficiency: Tested with NEWPORT1931-C.

The following abbreviations are used in the examples:

The preparation of embodiment 1 compound PHIR-AC-005

Step 1: Preparation of 6,6′-difluorobiphenyl-2,2′-dicarboxylic acid

Dissolve 75g of copper sulfate pentahydrate in 300ml of water, add 230ml of 25% ammonia water under stirring, and cool down to 0°C with an ice-salt bath. An aqueous solution prepared by 20.8 g of hydroxylamine hydrochloride and 12.8 g of sodium hydroxide was slowly added dropwise into the above cold copper solution, and kept below 0° C. for later use.

Mix 31g of 2-amino-3-fluorobenzoic acid and 85ml of concentrated hydrochloric acid, add 300ml of water and 60ml of acetonitrile, and cool down to below 0°C with an ice-salt bath, slowly drop the solution of 15.9g of sodium nitrite dissolved in 120ml of water Add to the above solution, stir and react at below 5°C for 1 hour, slowly add this clear diazonium solution dropwise into the reserved copper solution, and keep the temperature below 10°C during this process. Stir the reaction at room temperature for 1 hour, heat up to 85°C and add concentrated hydrochloric acid dropwise to acidify, cool down to 0°C in an ice-water bath to filter out the insoluble solid, wash the filter cake with water, and dry in vacuum to obtain 30.5g of 6,6'-difluoro Biphenyl-2,2'-dicarboxylic acid, off-white solid.

The second step: the preparation of 6,6'-difluorobiphenyl-2,2'-dicarboxylic acid methyl ester

Mix 30g of 6,6′-difluorobiphenyl-2,2′-dicarboxylic acid with 600ml of anhydrous methanol, heat up to reflux, slowly add 10ml of thionyl chloride dropwise, and react overnight under reflux to obtain a clear solution Concentrated to dryness under reduced pressure, the residue was separated and purified by silica gel column, and eluted with ethyl acetate and petroleum ether to obtain 29 g of methyl 6,6'-difluorobiphenyl-2,2'-dicarboxylate as white crystals.

Step 3: Preparation of (6,6′-difluorobiphenyl-2,2′-yl)dimethanol

15g of 6,6'-difluorobiphenyl-2,2'-dicarboxylate was dissolved in 400ml of dry THF, the clear solution was cooled to -5°C with an ice-salt bath, and 5.6g of Lithium aluminum hydride, insulated and stirred for 1 hour, slowly rose to room temperature, stirred and reacted for 12 hours, added water and 17ml of 15% aqueous sodium hydroxide solution dropwise to quench the reaction, suction filtered, and the filter cake was washed with THF. The filtrate was concentrated to dryness under reduced pressure, and the residue was separated and purified with a silica gel column to obtain 10 g of (6,6'-difluorobiphenyl-2,2'-yl)dimethanol as white crystals.

Step 4: Preparation of 2,2′-bis(bromomethyl)-6,6′-difluorobiphenyl

Dissolve 10.7g of (6,6'-difluorobiphenyl-2,2'-yl)dimethanol in 250ml of chloroform, slowly add 49g of phosphorus oxybromide in batches, heat up and reflux for 10 hours, and cool to room temperature , washed three times with saturated brine, the collected organic phase was dried with anhydrous sodium sulfate, filtered, the filtrate was concentrated to dryness under reduced pressure, and the residue was separated and purified by silica gel column to obtain 14.5 g of 2,2'-bis(bromomethyl) -6,6'-difluorobiphenyl, yellow oil.

Step 5: Preparation of 4,5-difluoro-9,10-dihydrophenanthrene

Dissolve 6.16g of 2,2′-bis(bromomethyl)-6,6′-difluorobiphenyl in 250ml of anhydrous ether, add 0.7g of magnesium powder and a grain of iodine under nitrogen protection, and heat to reflux for reaction For 1 hour, reflux under ultrasonic until the magnesium powder disappears, cool to room temperature, add a small amount of water, separate the ether phase, and wash with saturated brine, dry the organic phase with anhydrous _MgSO4 , filter, and concentrate the filtrate to dryness under reduced pressure. Separation and purification with a silica gel column gave 1.0 g of 4,5-difluoro-9,10-dihydrophenanthrene as a white solid.

Step 6: Preparation of 2-bromo-4,5-difluoro-9,10-dihydrophenanthrene

Dissolve 2.16g of 4,5-difluoro-9,10-dihydrophenanthrene in 150ml of chloroform, add 16.2mg of anhydrous ferric chloride, heat up to reflux, slowly add 1.95g of bromine dropwise and dissolve in 20ml The solution of chloroform was continued to reflux for 24 hours, cooled to room temperature, washed three times with saturated aqueous sodium bisulfite solution, the collected organic phase was dried with anhydrous sodium sulfate, filtered, the filtrate was concentrated to dryness under reduced pressure, and the residue was washed with a short Silica gel column decolorization, 2.8g of 2-bromo-4,5-difluoro-9,10-dihydrophenanthrene and 4,5-difluoro-9,10-dihydrophenanthrene mixture was obtained, which could not be separated and purified, and the GC content of the product It is 79%, yellow oil.

Step 7: Preparation of 2-(4,5-difluoro-9,10-dihydrophenanthrene-2-yl)-boronic acid pinacol ester

The 2-bromo-4,5-difluoro-9,10-dihydrophenanthrene mixture obtained in the sixth step of 2.8g, the pinacol ester of diboronic acid of 2.1g, the anhydrous potassium acetate of 1.1g, the Pd of 61mg ( dppf)Cl ₂ DCM palladium catalyst, and 50ml of N,N-dimethylformamide, heated to 85°C, stirred for 8 hours, cooled to room temperature, poured into ice water, extracted with ethyl acetate, used for organic phase Washed with saturated brine three times, the collected organic phase was dried with anhydrous sodium sulfate, filtered, the filtrate was concentrated to dryness under reduced pressure, and the residue was separated and purified by silica gel column to obtain 2.46 g of 2-(4,5-difluoro-9,10 -Dihydrophenanthrene-2-yl)-pinacol borate, white solid.

Step 8: Preparation of 2-(4,5-difluoro-9,10-dihydrophenanthrene-2-yl)pyridine

The 2.0g compound 2-(4,5-difluoro-9,10-dihydrophenanthrene-2-yl)-boronic acid pinacol ester obtained in the seventh step and 1.3g of 2-bromopyridine, 2.5g of Mix sodium carbonate water, 50ml toluene, 20ml ethanol and 20ml water, then add 65mg of catalyst Pd(PPh ₃ ) ₄ , under nitrogen protection, heat up and reflux for 12 hours, cool to room temperature, separate the organic phase and the water phase Extract with ethyl acetate, dry the organic phase, filter, and concentrate the filtrate to dryness under reduced pressure. The residue is separated and purified by silica gel column to obtain 1.5 g of 2-(4,5-difluoro-9,10-dihydrophenanthrene-2- base) pyridine, white solid.

Step 9: Preparation of Compound G-2

1.0g of compound 2-(4,5-difluoro-9,10-dihydrophenanthrene-2-yl)pyridine and 573mg of IrCl ₃ ·3H ₂ O were dispersed in 30ml of ethylene glycol ether and 10ml of water, under nitrogen Under protection, the temperature was raised to reflux for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water, and dried in vacuo to obtain 850 mg of compound G-2 as a yellow solid.

Step 10: Preparation of compound PHIR-AC-005

800mg of compound G-2, 98mg of acetylacetone and 520mg of anhydrous sodium carbonate were dispersed in 40ml of ethylene glycol ether, under the protection of nitrogen, the temperature was raised to reflux for 24 hours, cooled to room temperature, and the reaction solution was poured into water. It was extracted with DCM, the organic phase was dried and filtered, the filtrate was concentrated to dryness under reduced pressure, and the residue was separated and purified by silica gel column to obtain 650 mg of compound PHIR-AC-005 as a yellow solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.29-8.35(m,4H),8.14-8.21(m,4H),7.73-7.76(m,4H),7.63-7.69(m,2H),6.65- 6.69 (m, 2H), 5.01 (s, 1H), 2.59-2.63 (m, 4H), 2.83-2.90 (m, 4H), 1.64 (s, 6H).

(1) Glass transition temperature (DSC): 268.71°C;

(2) UV maximum absorption wavelength (DCM): 305nm, 335nm;

(3) Phosphorescence emission wavelength (DCM): 526nm

The preparation of embodiment 2 compound PHIR-AC-006

The first step: preparation of compound G-2

1.0g of compound 2-(4,5-bistrifluoromethyl-9,10-dihydrophenanthrene-2-yl)pyridine (refer to Example 1, the synthesis of the first to eight steps) and 427mg of IrCl ₃ . 3H ₂ O was dispersed in 30ml of ethylene glycol ether and 10ml of water, under the protection of nitrogen, the temperature was raised to reflux for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water, and dried in vacuum to obtain 520mg of compound G-2, a yellow solid .

The second step: the preparation of compound PHIR-AC-006

500mg of compound G-2, 62mg of acetylacetone and 262mg of anhydrous sodium carbonate were dispersed in 40ml of ethylene glycol ether, under the protection of nitrogen, the temperature was raised to reflux for 24 hours, cooled to room temperature, and the reaction solution was poured into water. It was extracted with DCM, the organic phase was dried and filtered, the filtrate was concentrated to dryness under reduced pressure, and the residue was separated and purified by silica gel column to obtain 300 mg of compound PHIR-AC-006 as a yellow solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.27-8.34(m,4H),8.14-8.21(m,4H),7.73-7.76(m,4H),7.63-7.68(m,2H),6.64- 6.68 (m, 2H), 5.01 (s, 1H), 2.59-2.63 (m, 4H), 2.83-2.90 (m, 4H), 1.66 (s, 6H).

(1) Glass transition temperature (DSC): 245.58°C;

(2) UV maximum absorption wavelength (DCM): 255nm, 305nm;

(3) Phosphorescence emission wavelength (DCM): 524nm

The preparation of embodiment 3 compound PHIR-AC-001

The first step: the preparation of 2-(4,5-difluorophenanthrene-2-yl)pyridine

1.5g of 2-(4,5-difluoro-9,10-dihydrophenanthrene-2-yl)pyridine prepared in the eighth step of Example 1 was dissolved in 100ml of benzene, 3.5g of DDQ was added, and heated to reflux for reaction After 3 days, it was cooled to room temperature, concentrated to dryness under reduced pressure, and the residue was separated and purified by a neutral alumina column to obtain 1.4 g of 2-(4,5-difluorophenanthrene-2-yl)pyridine as a white solid.

The second step: the preparation of compound G-2

Referring to the ninth step of Example 1, replace 2-(4,5-difluoro-9,10-dihydrophenanthrene-2-yl)pyridine with 2-(4,5-difluorophenanthrene-2-yl ) pyridine to obtain compound G-2, a yellow solid.

The third step: preparation of compound PHIR-AC-001

Referring to the method in the tenth step of Example 1, the compound PHIR-AC-001 was obtained as a yellow solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.30-8.37(m,4H),8.14-8.22(m,4H),7.73-7.76(m,4H),7.63-7.69(m,2H),7.50( s,4H), 6.64-6.68(m,2H), 5.01(s,1H), 1.64(s,6H).

(1) Glass transition temperature (DSC): 273.37°C;

(2) UV maximum absorption wavelength (DCM): 305nm, 335nm;

(3) Phosphorescence emission wavelength (DCM): 522nm

The preparation of embodiment 4 compound PHIR-CJH-001

872mg of PHIR-AC-001 and 2.9g of the compound 2-(4,5-difluorophenanthrene-2-yl)pyridine prepared in the first step in Example 2 were stirred and dispersed with 20ml of glycerin, and under nitrogen protection, Raise the temperature to 180°C, stir and react for 8 hours, cool to room temperature, pour the reaction solution into 100ml of 1N dilute hydrochloric acid, filter with suction, wash the filter cake with water, separate and purify the obtained solid with a silica gel column, and obtain 450mg of PHIR-CJH- 001, brown solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.31-8.36(m,6H),8.14-8.22(m,6H),7.73-7.76(m,6H),7.63-7.69(m,3H),7.51( s,6H),6.64-6.68(m,3H).

(1) Glass transition temperature (DSC): 288.56°C;

(2) UV maximum absorption wavelength (DCM): 305nm, 315nm, 335nm;

(3) Phosphorescence emission wavelength (DCM): 518nm

The preparation of embodiment 5 compound PHIR-PY-001

1.6 g of compound G-2 prepared in the second step of Example 2, 707 mg of 2-pyridinecarboxylic acid, 324 mg of anhydrous potassium carbonate, and 50 ml of 1,4-dioxane were heated and refluxed and stirred for 8 hours. Concentrate to dryness under reduced pressure, and the residue is separated and purified by silica gel column to obtain 0.8 g of compound PHIR-PY-001 as a yellow solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.31-8.36(m,4H),8.14-8.22(m,6H),7.73-7.76(m,4H),7.63-7.69(m,4H),7.50( s, 4H), 7.26-7.34 (m, 2H).

(1) Glass transition temperature (DSC): 287.39°C;

(2) UV maximum absorption wavelength (DCM): 305nm, 325nm, 355nm;

(3) Phosphorescence emission wavelength (DCM): 512nm

The preparation of embodiment 6 compound PHPT-AC-001

The first step: preparation of compound G-2

Compound 2-(4,5-difluorophenanthren- ₂ -yl)pyridine and 1.35g of K2PtCl4 prepared in the first step in the embodiment ₂ of 2.0g were dispersed in 60ml of ethylene glycol ether and 20ml of water, in Under the protection of nitrogen, the temperature was raised to 80°C and the reaction was stirred for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water, and dried in vacuum to obtain 1.8 g of compound G-2 as a brown solid.

The second step: the preparation of compound PHPT-AC-001

Take the compound G-21.0g obtained in step 1, 384mg of acetylacetone and 1g of anhydrous sodium carbonate and disperse in 20ml of ethylene glycol ether, under the protection of nitrogen, heat up to 100°C and stir for 24 hours, cool to room temperature, and filter , the filter cake was washed with water, then dissolved in DCM, filtered, the filtrate was dried, filtered, and the filtrate was concentrated to dryness under reduced pressure to obtain 420 mg of compound PHPT-AC-001 as a dark yellow solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.34(s,1H),8.14-8.22(m,2H),7.73-7.76(m,2H),7.63-7.69(m,2H),7.50(s, 2H), 6.68(s,1H), 5.01(s,1H), 1.64(s,6H).

(1) Glass transition temperature (DSC): 258.06°C;

(2) UV maximum absorption wavelength (DCM): 305nm, 315nm, 335nm;

(3) Phosphorescence emission wavelength (DCM): 533nm

Preparation of Example 7 Compound PHPT-AC-006

Referring to Example 6, replace 2-(4,5-difluorophenanthrene-2-yl)pyridine with 2-(4,5-bistrifluoromethyl-9,10-dihydrophenanthrene-2-yl)pyridine , Compound PHPT-AC-006 was prepared as a brown solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.36(s,1H),8.13-8.17(m,2H),7.72-7.76(m,2H),7.63-7.69(m,2H),6.77(s, 1H), 5.01(s, 1H), 2.59-2.63(m, 2H), 2.83-2.90(m, 2H), 1.66(s, 6H).

(1) Glass transition temperature (DSC): 246.39°C;

(2) UV maximum absorption wavelength (DCM): 255nm, 305nm, 325nm;

(3) Phosphorescence emission wavelength (DCM): 535nm

Preparation of Example 8 Compound PHPT-AC-014

Referring to Example 6, replace 2-(4,5-difluorophenanthrene-2-yl)pyridine with 2-(7-methyl-4,5-bistrifluoromethyl-9,10-dihydrophenanthrene- 2-yl)pyridine, the prepared compound PHPT-AC-014, brown solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.27-8.34(m,2H),8.14(s,1H),7.73-7.76(m,2H),7.63-7.68(m,1H),6.64-6.68( m, 1H), 5.01(s, 1H), 2.59-2.63(m, 2H), 2.83-2.90(m, 2H), 2.63(s, 3H), 1.64(s, 6H).

(1) Glass transition temperature (DSC): 242.52°C;

(2) UV maximum absorption wavelength (DCM): 255nm, 305nm, 325nm;

(3) Phosphorescence emission wavelength (DCM): 532nm

Preparation of Example 9 Compound PHPT-AC-016

Referring to Example 6, replace 2-(4,5-difluorophenanthrene-2-yl)pyridine with 2-(4,5-dimethoxy-7-methyl-9,10-dihydrophenanthrene-2 -yl)pyridine, to prepare compound PHPT-AC-016, brown solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.32(s,1H),8.16-8.19(m,2H),7.73-7.76(m,2H),7.64(s,1H),6.92(s,1H) ,5.00(s,1H),2.59-2.64(m,2H),2.83-2.89(m,2H),2.64(s,3H),1.64(s,6H).

(1) Glass transition temperature (DSC): 358.05°C;

(2) UV maximum absorption wavelength (DCM): 305nm, 315nm, 325nm;

(3) Phosphorescence emission wavelength (DCM): 542nm

Preparation of Example 10 Compound PHPT-AC-022

Referring to Example 6, replace 2-(4,5-difluorophenanthrene-2-yl)pyridine with 2-(3,6-difluoro-4,5-bistrifluoromethyl-9,10-dihydro phenanthrene-2-yl)pyridine, compound PHPT-AC-022 was prepared, brown solid.

Experimental data:

¹ H NMR(CDCl ₃ ,300MHz):δ=8.34(s,1H),8.14-8.18(m,2H),7.73-7.76(m,2H),6.96(m,1H),5.00(s,1H) ,2.59-2.63(m,2H),2.84-2.89(m,2H),1.65(s,6H).

(1) Glass transition temperature (DSC): 242.95°C;

(2) UV maximum absorption wavelength (DCM): 255nm, 305nm, 325nm;

(3) Phosphorescence emission wavelength (DCM): 526nm

Example 11 Preparation of devices OLED-1, OLED-2, OLED-3

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

Among them, the structural formula of TDATA is as follows:

3) Continue to vapor-deposit NPB on the above-mentioned hole-injection layer as a hole-transport layer, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10nm;

Wherein, the structural formula of NPB is as follows:

4) Continue to evaporate a layer of compound PHIR-AC-001 and CBP shown in formula I on the hole transport layer as the organic light-emitting layer of the device. The evaporation rate ratio of compound PHIR-AC-001 and CBP is 1:100, The amount of compound PHIR-AC-001 is 5% of the mass of CBP, the evaporation rate is 0.1nm/s, and the film thickness of the organic light-emitting layer obtained by evaporation is 50nm;

5) Continue to evaporate a layer of Alq3 material on the organic light-emitting layer as the electron transport layer of the device, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 20nm;

Wherein, the structural formula of Alq3 is as follows:

6) A magnesium/silver alloy layer is sequentially evaporated on the electron transport layer as the cathode layer of the device. The evaporation rate of the magnesium/silver alloy layer is 2.0-3.0nm/s, and the thickness of the evaporated film is 100nm. Magnesium and silver The mass ratio is 1:9, and the device OLED-1 provided by the present invention is obtained.

Follow the same steps as above, only replace PHIR-AC-001 used in step 4) with PHIR-AC-005 to obtain OLED-2 provided by the present invention;

Following the same steps as above, only the PHIR-AC-001 used in step 4) was replaced with PHIR-AC-006 to obtain the OLED-3 provided by the present invention.

The performance testing results of the obtained devices OLED-1 to OLED-3 are shown in Table 1.

Table 1. Performance test results of OLED-1 to OLED-3

It can be known from the above that the current density of the organic light-emitting device obtained by doping 5% of the compound shown in formula I exceeds 2100A/m ² , the power efficiency is as high as 6.92cd/A, and the light color is relatively pure green light.

Example 12 Preparation of Devices OLED-4～OLED-8

Prepared according to the method of Example 11, only PHIR-AC-001 was replaced by PHPT-AC-001, PHPT-AC-006, PHPT-AC-014, PHPT-AC-016, PHPT-AC-022 in order to obtain the device OLED-4～OLED-8.

The performance of the device is detailed in Table 2:

Table 2. Performance test results of OLED-4 to OLED-8

It can be seen from the above that the organic light-emitting device obtained by doping 5% of the compound shown in formula I has higher current density, significantly improved power efficiency, and the light color is relatively pure green light.

Although the present invention has been described in conjunction with preferred embodiments, the present invention is not limited to the above-mentioned embodiments, it should be understood that under the guidance of the present invention, those skilled in the art can make various modifications and improvements, and the appended claims summarize scope of the present invention.

Claims (31)

1. the compound shown in formula I, In the formula I, R ₁ , R ₄ and R ₅ are all selected from hydrogen atom, fluorine atom, methoxy group, cyano group, trifluoromethoxy group, C1-C50 aliphatic hydrocarbon group, C1-C50 aromatic group and Any one of C1-C50 fused ring aromatic groups; R2 is selected from any one of a _hydrogen atom, a fluorine atom, a trifluoromethyl group, a methoxy group and an aliphatic hydrocarbon group of C1-C50; M is an iridium or platinum atom; Z is -CH ₂ CH ₂ - or -CH=CH-; X is 1 or 2; When X is 1 or ₂ , R is acetylacetonate, C1-C50 aliphatic hydrocarbon substituted acetoacetyl, 2-pyridineformyloxy or 2-pyridineformyloxy containing substituents; In the 2-pyridinecarboxy group of the substituent, the substituent is selected from any one of a fluorine atom, a C1-C10 alkyl group, a cyano group and a trifluoromethyl group. 2. The compound according to claim ₁ , characterized in that: R is selected from methyl. 3. The compound according to claim 1 or 2, characterized in that: the compound shown in the formula I is any one of the compounds shown in the formula I-1a, the formula I-1b, the formula I-2a and the formula I-2b kind: In the formula I-1a, formula I-1b, formula I-2a and formula I-2b, the definitions of R ₁ , R ₂ , R ₄ , R ₅ and Z are the same as those of R ₁ and R ₂ in formula I in claim 1 , R ₄ , R ₅ , M and Z have the same definitions; In the formula I-1a and formula I-1b, M is a platinum atom; in the formula I-2a and formula I-2b, M is an iridium atom; The R ₇ are all C1-C50 aliphatic hydrocarbon groups; The R ₈ is any one selected from a hydrogen atom, a fluorine atom, a C1-C10 alkyl group, a cyano group and a trifluoromethyl group. 4. The compound according to claim 3, characterized in that: said formula I-1a is a compound shown in PHPT-AC-I: The formula I-2a is a compound shown in PHIR-AC-I: The formula I-2b is a compound shown in PHIR-PY-I: In the PHPT-AC-I, PHIR-AC-I and PHIR-PY-I, the definitions of R ₁ to R ₅ and Z are the same as the definitions of R ₁ to R ₅ and Z in formula I in claim 1. 5. The compound according to claim 4, characterized in that: The compound shown in the PHIR-AC-I is any one of the following compounds: The compound shown in the PHPT-AC-I is any one of the following compounds: The compound shown in the PHIR-PY-I is any one of the following compounds: 6. The compound shown in formula I-3, In the formula I-3, R ₁ , R ₄ and R ₅ are all selected from hydrogen atom, fluorine atom, methoxy group, cyano group, trifluoromethoxy group, C1-C50 aliphatic hydrocarbon group, C1-C50 aromatic Any one of the condensed ring aromatic groups of C1-C50; R2 is selected from any one of a _hydrogen atom, a fluorine atom, a trifluoromethyl group, a methoxy group and an aliphatic hydrocarbon group of C1-C50; M is an iridium atom; Z is _-CH2CH2- or -CH= _CH- . 7. The compound shown in formula I-3 according to claim 6, characterized in that: R ₂ is selected from methyl. 8. The compound shown in formula I-3 according to claim 6, characterized in that: said formula I-3 is a compound shown in PHIR-CJH-I: In the formula PHIR-CJH-I, the definitions of R ₁ to R ₅ and Z are the same as the definitions of R ₁ to R ₅ and Z in the formula I-3 in claim 6. 9. the compound shown in formula I-3 according to claim 8, is characterized in that: the compound shown in described PHIR-CJH-I is any one in the following compounds: 10. A luminescent material containing the compound represented by formula I according to any one of claims 1-5 or containing the compound represented by formula I-3 according to any one of claims 6-9. 11. The luminescent material according to claim 10, characterized in that: the luminescent material is an organic electrophosphorescent luminescent material. 12. The luminescent material according to claim 10, characterized in that: the luminescent wavelength of the luminescent material is 460-620 nm. 13. Use of the compound represented by formula I according to any one of claims 1-5 or the compound represented by formula I-3 according to any one of claims 6-9 in the preparation of luminescent materials. 14. The application according to claim 13, characterized in that the luminescent material is an organic electrophosphorescent luminescent material. 15. The application according to claim 13, characterized in that: the luminescent wavelength of the luminescent material is 460-620nm. 16. the compound shown in the formula I described in any one of claim 1-5 or the compound shown in the formula I-3 described in any one of claim 6-9 as light-emitting layer in the preparation of organic electroluminescence device application. 17. The application according to claim 16, characterized in that the organic electroluminescent device is an organic electroluminescent device. 18. The application according to claim 17, characterized in that: the organic electroluminescent device is an organic electroluminescent orange phosphorescent material. 19. The application according to claim 18, characterized in that: the luminescent wavelength of the luminescent material is 460-620nm. 20. The application according to claim 16, characterized in that: the organic electroluminescent device is sequentially composed of a transparent substrate, an anode, a hole injection layer, a hole transport layer, an organic light-emitting layer, and an electron transport layer from bottom to top. and cathode layer composition; Wherein, the material constituting the transparent substrate is glass or a flexible substrate; The material constituting the anode layer is an inorganic material or an organic conductive polymer; wherein the inorganic material is indium tin oxide, zinc oxide, tin zinc oxide, gold, silver or copper; the organic conductive polymer is selected from polythiophene , at least one of sodium polyvinylbenzenesulfonate and polyaniline; The material constituting the hole injection layer is TDATA; The structural formula of the TDATA is as follows: The material constituting the hole transport layer is NPB; The structural formula of the NPB is as follows: The material constituting the organic light-emitting layer is the compound shown in formula I described in any one of claims 1-5 or the compound shown in formula I-3 described in any one of claims 6-9 and a host material; Wherein, the host material is mCP, CBP, NATZ or Among them, the structural formulas of mCP, CBP and NATZ are as follows: The mass of the compound shown in formula I described in any one of claims 1-5 or the compound shown in formula I-3 described in any one of claims 6-9 is 1-10% of the mass of the host material; The material constituting the electron transport layer is Alq3, Gaq3 or BPhen; Among them, the structural formulas of Alq3, Gaq3 and BPhen are as follows: The material constituting the cathode layer is selected from any one of the following elements or an alloy of any two or fluorides of the following elements: lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold and silver. 21. The application according to claim 20, characterized in that: the compound shown in formula I according to any one of claims 1-5 or the compound shown in formula I-3 according to any one of claims 6-9 The mass of the compound is 5% of the mass of the host material. 22. The application according to claim 20, characterized in that: The thickness of the hole injection layer is 30-50nm; The thickness of the hole transport layer is 5-15nm; The thickness of the organic light-emitting layer is 10-100nm; The thickness of the electron transport layer is 10-30nm; The thickness of the cathode layer is 90-110nm. 23. The application according to claim 22, characterized in that: The thickness of the hole injection layer is 40nm; The thickness of the hole transport layer is 10nm; The thickness of the organic light-emitting layer is 50nm; The thickness of the electron transport layer is 20nm; The thickness of the cathode layer is 100 nm. 24. contain the compound shown in the formula I described in any one of claim 1-5 or contain the compound shown in the formula I-3 described in any one of claim 6-9 as the organic electroluminescent device of emissive layer . 25. The organic electroluminescent device according to claim 24, characterized in that: the organic electroluminescent device is an organic electroluminescent device. 26. The organic electroluminescent device according to claim 25, characterized in that: the organic electroluminescent device is an organic electroluminescent orange phosphorescent material. 27. The organic electroluminescent device according to claim 26, characterized in that: the luminescent wavelength of the luminescent material is 460-620nm. 28. The organic electroluminescent device according to claim 24, characterized in that: the organic electroluminescent device is sequentially composed of a transparent substrate, an anode, a hole injection layer, a hole transport layer, and an organic light-emitting layer from bottom to top. , electron transport layer and cathode layer; Wherein, the material constituting the transparent substrate is glass or a flexible substrate; The material constituting the anode layer is an inorganic material or an organic conductive polymer; wherein the inorganic material is indium tin oxide, zinc oxide, tin zinc oxide, gold, silver or copper; the organic conductive polymer is selected from polythiophene , at least one of sodium polyvinylbenzenesulfonate and polyaniline; The material constituting the hole injection layer is TDATA; The structural formula of the TDATA is as follows: The material constituting the hole transport layer is NPB; The structural formula of the NPB is as follows: The material constituting the organic light-emitting layer is the compound shown in formula I described in any one of claims 1-5 or the compound shown in formula I-3 described in any one of claims 6-9 and a host material; Wherein, the host material is mCP, CBP, NATZ or Among them, the structural formulas of mCP, CBP and NATZ are as follows: The mass of the compound shown in formula I described in any one of claims 1-5 or the compound shown in formula I-3 described in any one of claims 6-9 is 1-10% of the mass of the host material; The material constituting the electron transport layer is Alq3, Gaq3 or BPhen; Among them, the structural formulas of Alq3, Gaq3 and BPhen are as follows: The material constituting the cathode layer is selected from any one of the following elements or an alloy of any two or fluorides of the following elements: lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold and silver. 29. The organic electroluminescent device according to claim 28, characterized in that: the compound shown in formula I according to any one of claims 1-4 or the formula I according to any one of claims 5-7 The mass of the compound shown in -3 is 5% of the mass of the host material. 30. The organic electroluminescent device according to claim 29, characterized in that: The thickness of the hole injection layer is 30-50nm; The thickness of the hole transport layer is 5-15nm; The thickness of the organic light-emitting layer is 10-100nm; The thickness of the electron transport layer is 10-30nm; The thickness of the cathode layer is 90-110nm. 31. The organic electroluminescent device according to claim 30, characterized in that: The thickness of the hole injection layer is 40nm; The thickness of the hole transport layer is 10nm; The thickness of the organic light-emitting layer is 50nm; The thickness of the electron transport layer is 20nm; The thickness of the cathode layer is 100 nm.