CN109608500B - Organic electroluminescent compound, preparation and application thereof, and electroluminescent device comprising organic electroluminescent compound - Google Patents

Organic electroluminescent compound, preparation and application thereof, and electroluminescent device comprising organic electroluminescent compound Download PDF

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CN109608500B
CN109608500B CN201711275523.7A CN201711275523A CN109608500B CN 109608500 B CN109608500 B CN 109608500B CN 201711275523 A CN201711275523 A CN 201711275523A CN 109608500 B CN109608500 B CN 109608500B
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organic electroluminescent
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electroluminescent compound
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CN109608500A (en
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曹建华
董梁
张建川
王士波
隋岩
华瑞茂
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0086—Platinum compounds
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs

Abstract

The invention discloses an organic electroluminescent compound, which has a structural formula shown as the following formula:
Figure DDA0001496453470000011
the organic electroluminescent compound has good chemical stability and high glass transition temperature and decomposition temperature of the material, and is an OLED material with excellent performance. The synthesis route of the material is simple and easy to operate, the reaction yield is high, the preparation cost of the OLED material can be reduced, and the material has a good industrial prospect. The OLED material can be used as a dopant of a light-emitting layer in an organic electroluminescent device. The organic electroluminescent diode prepared by the OLED material can realize the effects of high brightness, high efficiency and low voltage, can effectively avoid screen dark spots and has more excellent performance.

Description

Organic electroluminescent compound, preparation and application thereof, and electroluminescent device comprising organic electroluminescent compound
Technical Field
The invention relates to the technical field of organic electroluminescent display. And more particularly, to an organic electroluminescent compound, preparation and use thereof, and an electroluminescent device comprising the same.
Background
Organic electroluminescence (abbreviated as OLED) and related research firstly discovered the electroluminescence phenomenon of organic compound single crystal anthracene in pope et al as early as 1963. Kodak company of the United states of 1987 made an amorphous film device by evaporating small organic molecules, and reduced the driving voltage to within 20V. The device has the advantages of ultra-light weight, full curing, self luminescence, high brightness, wide viewing angle, high response speed, low driving voltage, low power consumption, bright color, high contrast, simple process, good temperature characteristic, soft display and the like, and can be widely applied to flat panel displays and surface light sources, so the device is widely researched, developed and used.
Organic electroluminescence is largely divided into fluorescence and phosphorescence, but according to the spin quantum statistical theory, the probability of singlet excitons and triplet excitons is 1:3, i.e., the theoretical limit of fluorescence from radiative transition of singlet excitons is 25, and the theoretical limit of fluorescence from radiative transition of triplet excitons is 75. It is urgent to use 75% of the energy of triplet excitons. Forrest et al discovered in 1997 that the phosphorescence electroluminescence phenomenon breaks through the limit of 25% efficiency of the quantum efficiency of the organic electroluminescence material, and arouses people to pay extensive attention to the metal complex phosphorescence material.
Therefore, it is required to provide an organic electroluminescent compound which can emit phosphorescence, has high luminous efficiency, and has stable performance.
Disclosure of Invention
The first object of the present invention is to provide an organic electroluminescent compound, which is a phosphorescent material and can emit red orange light, and has high luminous efficiency, high brightness and good stability.
The second object of the present invention is to provide a method for preparing an organic electroluminescent compound.
The third purpose of the invention is to provide an application of the organic electroluminescent compound.
It is a fourth object of the invention to provide an electroluminescent device.
In order to achieve the first object, the present invention provides an organic electroluminescent compound, which has a structural formula shown in formula I below:
Figure BDA0001496453450000011
wherein:
Ar1any one selected from the following groups:
Figure BDA0001496453450000021
Ar2any one selected from the following groups:
Figure BDA0001496453450000022
R1、R2、R3、R4、R5、R6、R7、R8、R9and R10Each independently selected from any one of H, -F, -CN, alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, linear alkylene with 2-15 carbon atoms, alkyl with 1-15 fluorinated carbon atoms, alkoxy with 1-15 fluorinated carbon atoms and linear alkylene with 2-15 fluorinated carbon atoms;
z is selected from O or S;
m is selected from Ir or Pt;
l is any one of acetylacetone group, acetoacetyl group with branch chain with 5-25 carbon atoms in total, and straight chain acetoacetyl group with 5-25 carbon atoms in total;
x is 1 or 2 or 3;
y is 0 or 1 or 2 or 3;
Figure BDA0001496453450000023
represents a substitution bit;
represents a coordinate bond.
Preferably, the total number of carbon atoms in the alkyl group is 1 to 15 selected from the group consisting of C-C alkyl, C-, One of C1-C10 alkyl, C1-C2 alkyl and C2-C3 alkyl.
Preferably, the alkoxy groups with the total number of carbon atoms of 1-15 are selected from C2-C15, C3-C15, C15-C15, C15-C36, One of C1-C10 alkoxy, C2-C10 alkoxy, C3-C10 alkoxy, C1-C10 alkoxy, C1-C2 alkoxy and C2-C3 alkoxy;
preferably, the linear alkylene group with the total number of carbon atoms of 2 to 15 is selected from one of C3 to C15 linear alkylene group, C4 to C15 linear alkylene group, C5 to C15 linear alkylene group, C6 to C15 linear alkylene group, C1 to C6 linear alkylene group, C2 to C6 linear alkylene group, C3 to C6 linear alkylene group, C4 to C6 linear alkylene group, C5 to C6 linear alkylene group, C2 to C5 linear alkylene group, C3 to C5 linear alkylene group, C4 to C5 linear alkylene group, C2 to C4 linear alkylene group, C3 to C4 linear alkylene group, C4 to C4 linear alkylene group and C4 to C4 linear alkylene group;
preferably, the fluorinated alkyl group having 1 to 15 carbon atoms in total is selected from the group consisting of C2-C15 fluorinated alkyl group, C3-C15 fluorinated alkyl group, C4-C15 fluorinated alkyl group, C5-C15 fluorinated alkyl group, C6-C15 fluorinated alkyl group, C1-C7 fluorinated alkyl group, C2-C7 fluorinated alkyl group, C3-C7 fluorinated alkyl group, C4-C7 fluorinated alkyl group, C5-C7 fluorinated alkyl group, C7-C7 alkyl group, C7 fluorinated alkyl group, C7-C7 alkyl group, One of fluorinated alkyl of C1-C4, fluorinated alkyl of C2-C4, fluorinated alkyl of C3-C4, fluorinated alkyl of C1-C3, fluorinated alkyl of C1-C10, fluorinated alkyl of C2-C10, fluorinated alkyl of C3-C10, fluorinated alkyl of C1-C10, fluorinated alkyl of C1-C2 and fluorinated alkyl of C2-C3;
preferably, the fluorinated alkoxy group having 1 to 15 carbon atoms in total is selected from the group consisting of C2 to C15 fluorinated alkoxy group, C3 to C15 fluorinated alkoxy group, C4 to C15 fluorinated alkoxy group, C5 to C15 fluorinated alkoxy group, C6 to C15 fluorinated alkoxy group, C1 to C7 fluorinated alkoxy group, C2 to C7 fluorinated alkoxy group, C3 to C7 fluorinated alkoxy group, C4 to C7 fluorinated alkoxy group, C5 to C7 fluorinated alkoxy group, C6 to C7 fluorinated alkoxy group, C1 to C6 fluorinated alkoxy group, C2 to C6 fluorinated alkoxy group, C3 to C6 fluorinated alkoxy group, C6 to C6 fluorinated alkoxy group, C6 to C6 alkoxy group, One of C3-C5 fluorinated alkoxy, C4-C5 fluorinated alkoxy, C1-C4 fluorinated alkoxy, C2-C4 fluorinated alkoxy, C3-C4 fluorinated alkoxy, C1-C3 fluorinated alkoxy, C1-C10 fluorinated alkoxy, C2-C10 fluorinated alkoxy, C3-C10 fluorinated alkoxy, C1-C10 fluorinated alkoxy, C1-C2 fluorinated alkoxy and C2-C3 fluorinated alkoxy;
preferably, the fluorinated linear olefin group having a total number of carbon atoms of 2 to 15 is selected from the group consisting of a fluorinated linear olefin group of C3 to C15, a fluorinated linear olefin group of C4 to C15, a fluorinated linear olefin group of C15 to C15, One of a fluorinated linear olefin group of C2-C8 and a fluorinated linear olefin group of C2-C3.
Preferably, the structural formula of the organic electroluminescent compound with the structural formula I is specifically shown as any one of the following formulas OR-1 to OR-164:
Figure BDA0001496453450000041
Figure BDA0001496453450000051
Figure BDA0001496453450000061
Figure BDA0001496453450000071
Figure BDA0001496453450000081
Figure BDA0001496453450000091
Figure BDA0001496453450000101
wherein: z is selected from O or S;
n is selected from 1-8, and n is a positive integer.
A second object of the present invention is to provide a method for preparing an organic electroluminescent compound, the method comprising the steps of:
has a structural formula of
Figure BDA0001496453450000102
The ligand A and the alkali are subjected to coordination reaction in the presence of alkali to obtain the organic electroluminescent compound shown in the formula I:
Figure BDA0001496453450000103
wherein:
Ar1any one selected from the following groups:
Figure BDA0001496453450000104
Ar2any one selected from the following groups:
Figure BDA0001496453450000105
Figure BDA0001496453450000111
R1、R2、R3、R4、R5、R6、R7、R8、R9and R10Each independently selected from any one of H, -F, -CN, alkyl with 1-15 carbon atoms, alkoxy with 1-15 carbon atoms, linear alkylene with 2-15 carbon atoms, alkyl with 1-15 fluorinated carbon atoms, alkoxy with 1-15 fluorinated carbon atoms and linear alkylene with 2-15 fluorinated carbon atoms;
z is selected from O or S;
m is selected from Ir or Pt;
a is selected from acetylacetone, branched acetoacetyl with 5-25 carbon atoms in total, and linear acetoacetyl with 5-25 carbon atoms in total;
x is 1 or 2 or 3;
y is 0 or 1 or 2 or 3;
Figure BDA0001496453450000112
represents a substitution bit;
represents a coordinate bond.
Preferably, in the preparation method, when x in the structural formula of formula I in the organic electroluminescent compound of formula I is 1 or 2, the structural formula is
Figure BDA0001496453450000113
The molar ratio of the compound of (1) to L is 1: 2-4. For example, the molar ratio of the two may include, but is not limited to, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, and the like; structural formula is
Figure BDA0001496453450000114
The molar ratio of the compound (b) to the base is 1: 5-15. For example, the molar ratio of the two may include, but is not limited to, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, and the like.
Preferably, in the preparation method, when x in the structural formula of formula I in the organic electroluminescent compound of formula I is 3, the structural formula is
Figure BDA0001496453450000121
The molar ratio of the compound of (1) to L is 1: 1-1.5. For example, the molar ratio of the two can include, but is not limited to, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, and the like.
Preferably, the base is selected from sodium or potassium carbonate.
Preferably, the coordination reaction is carried out in a solvent selected from one or more of ethylene glycol ethyl ether, glycerol, acetonitrile and chloroform.
Preferably, the coordination reaction is carried out under an inert atmosphere at a temperature of 150 ℃ to 200 ℃ for a period of 8 to 24 hours. In some embodiments, the temperature of the reaction may include, but is not limited to, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, and the like. The reaction time is more preferably 10 to 16 hours.
Preferably, the structural formula is
Figure BDA0001496453450000122
The preparation of the compound of (1) may comprise the steps of:
1) r is to be2-CHO and the formula
Figure BDA0001496453450000123
The compound is evenly mixed in a solvent, trifluoroacetic acid is dripped into the mixture to carry out condensation addition reaction, and the compound with the structural formula as shown in the specification is obtained after the reaction is finished
Figure BDA0001496453450000124
A compound of (1);
2) the structural formula obtained in the step 1) is shown as
Figure BDA0001496453450000125
The compound and palladium/carbon are mixed evenly in a solvent for dehydrogenation and oxidation reaction to obtain the compound with the structural formula as shown in the specification
Figure BDA0001496453450000126
A compound of (1);
3) the structural formula obtained in the step 2) is shown as
Figure BDA0001496453450000127
Compound of (A), Ar1Mixing W (F, Cl, Br, I) with inorganic base to perform coupling reaction to obtain the compound with the structural formula
Figure BDA0001496453450000128
A compound of (1);
4) the structural formula obtained in the step 3) is shown as
Figure BDA0001496453450000129
The compound of (A) and the salt of the metal M are subjected to coordination reaction, and the compound of formula (I) is obtained after the reaction is finished
Figure BDA0001496453450000131
The compound of (1).
Preferably, in the step 1), the R2-CHO、
Figure BDA0001496453450000132
And the feeding molar amount of trifluoroacetic acid is 1.0: 1.0-1.5:1.0-1.5, more preferably 1.0: 1.0: 1.0.
preferably, in the step 1), in the condensation addition reaction step, the reaction temperature is 0-40 ℃ and the reaction time is 8-16 hours, preferably 12 hours.
Preferably, in the step 2),
Figure BDA0001496453450000133
the feeding mass and the dosage of palladium/carbon are 1.0: 0.01-1.0, in particular 1.0: 0.02; in the step of dehydrogenation oxidation reaction, the temperature is 120-140 ℃, and the time is 12-48 hours, specifically 24 hours;
preferably, in the step 3),
Figure BDA0001496453450000134
the charging molar ratio of R1-W (W ═ F, GI, Br, I) to the inorganic base is 1.0: 1.0-2.0: 1.0-2.0. More preferably 1.0: 1.2: 1.2, 1.0: 1.3: 1.3, 1.0: 1.4: 1.4, 1.0: 1.5: 1.5, 1.0: 1.1: 1.2 or 1.0: 1.2: 1.5.
preferably, in the step 3), the inorganic base may be at least one of sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium tert-butoxide, and potassium tert-butoxide;
preferably, in the step 3), the temperature of the coupling reaction is 0-80 ℃ and the time is 12-48 hours, preferably 24 hours.
Preferably, in the step 4),
Figure BDA0001496453450000135
the molar ratio of the metal salt is 1: 0.2-2. Can be specifically represented by
Figure BDA0001496453450000136
The molar ratio of the metal to the trivalent metal (such as iridium trichloride) can be 1:0.2, 1:0.3, 1:0.4, 1:0.5 and 1: 0.6; compound (I)
Figure BDA0001496453450000137
The molar ratio of the metal to the divalent metal (e.g., potassium tetrachloroplatinate) can beIs 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, etc.; the solvent is glycol ethyl ether and water, and the volume ratio of the water to the glycol ethyl ether is 1:1-5, and the specific volume ratio can be 1:2, 1:3, 1:4, 1:5, and preferably 1:3.
Preferably, in the step 4), the temperature of the coordination reaction is 80-110 ℃, specifically 80-85 ℃, 85-90 ℃, 90-95 ℃, 95-100 ℃, 100-110 ℃, and more preferably 95-100 ℃; the reaction time is 8 to 20 hours, more preferably 10 to 12 hours.
Preferably, in the step 4), the salt of the metal M is selected from iridium trichloride or potassium tetrachloroplatinate.
Wherein the structural formula is
Figure BDA0001496453450000141
In the preparation method of the compound of (1), the R1、R2、R3、R4、Ar1、Ar2M, x are defined as the same as the corresponding symbols in the structural formula of the organic electroluminescent compound and are not repeated here.
To achieve the third object, the present invention provides the use of the above organic electroluminescent compounds for the preparation of electroluminescent devices.
Preferably, the electroluminescent device is an organic light emitting diode.
To achieve the fourth object, the present invention provides an electroluminescent device comprising the above organic electroluminescent compound.
Preferably, the electroluminescent device is an organic light emitting diode.
Preferably, the organic electroluminescent compound is a material constituting an organic light emitting layer of the electroluminescent device.
Preferably, the electroluminescent device may specifically have the following structure:
the organic electroluminescent device sequentially comprises a transparent substrate, an anode, a hole transport layer, an organic light-emitting layer, an electron transport layer and a cathode layer from bottom to top.
Preferably, the material constituting the transparent substrate is glass or a flexible substrate;
preferably, 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 conducting polymer is selected from at least one of polythiophene, sodium polyvinyl benzene sulfonate and polyaniline;
preferably, the materials for forming the hole injection layer and the hole transport layer are BNP, PEDOT PSS, TAPC or PDNA;
preferably, the BNP, PEDOT: PSS, TAPC or PDNA has the following structural formula:
Figure BDA0001496453450000142
preferably, the material for forming the organic light-emitting layer is a compound represented by formula I or a mixture of the compound represented by formula I and a phosphorescent host material; when the material for forming the organic light-emitting layer is a mixture of the compound shown in the formula I and the phosphorescent host material, the mass ratio of the compound shown in the formula I to the phosphorescent host material is 0.001-0.2:1, and preferably 0.02: 1.
Preferably, the phosphorescent Host material is one of PVK, CBP, CDBP, TRZ, 26 DCZPy, BBCP, TZPPI, Host-D and SiMCP.
Preferably, the structural formulas of PVK, CBP, CDBP, TRZ, 26DCZPPY, BBCP, TZPPI, Host-D and SiMCP are respectively as follows:
Figure BDA0001496453450000151
preferably, the material constituting the electron transport layer is one of Alq3, Gaq3, and TPBI.
Wherein the structural formulas of Alq3, TPBI and Gaq3 are as follows in sequence:
Figure BDA0001496453450000152
preferably, the cathode layer is made of a material selected from any one or an alloy of any two of the following elements or fluorides of the following elements: lithium, magnesium, silver, calcium, strontium, aluminum, indium, copper, gold, and silver.
Preferably, the hole injection layer has a thickness of 5nm to 15nm, and more preferably 10 nm.
Preferably, the hole transport layer has a thickness of 5nm to 15nm, and more preferably 10 nm.
Preferably, the thickness of the organic light emitting layer is 10nm to 100nm, and more preferably 20nm to 80 nm.
Preferably, the thickness of the electron transport layer is 40 to 60nm, and more preferably 50 nm.
Preferably, the cathode layer has a thickness of 90nm to 110nm, and more preferably 100 nm.
The invention has the following beneficial effects:
the organic electroluminescent compound is a phosphorescent material, and can emit red orange light with high efficiency and high stability. Meanwhile, the organic electroluminescent compound has good chemical stability, and the glass transition temperature and the decomposition temperature of the organic electroluminescent compound are both more than 300 ℃, so that the organic electroluminescent compound is an OLED material with excellent performance. The organic electroluminescent compound has the advantages of simple preparation method, easily obtained raw materials, low preparation cost and high overall reaction yield.
The organic electroluminescent compound can be used for organic electroluminescent equipment, and has important application value for the development and application of illumination and flat panel display. The red-orange light device can be prepared by mixing with a main material and evaporating equipment, or the red-orange light device can be prepared by evaporating a single-layer film, and then the white light illumination equipment can be prepared by matching with a blue light emitting layer, and the red-orange light device can also be used as a dopant of the light emitting layer in an organic electroluminescent device. The organic electroluminescent diode prepared by the organic electroluminescent compound can realize the effects of high brightness, high efficiency and low voltage, can effectively avoid screen dark spots and has more excellent performance.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a preparation of an organic electroluminescent compound obtained in example 11H-NMR spectrum.
FIG. 2 shows the phosphorescence maximum emission wavelength of the organic electroluminescent compound obtained in example 2.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the embodiment of the invention, the performance detection conditions of the prepared electroluminescent device are as follows:
luminance and chromaticity coordinates: testing with a photosresearch PR-715 spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: tested using NEWPORT 1931-C.
Example 1 synthesis of organic electroluminescent compound OR-1:
Figure BDA0001496453450000161
step 1: synthesis of the compound 1-phenyl-2, 3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole:
Figure BDA0001496453450000162
5.85g (55mmol) of benzaldehyde, 8.8g (55mmol) of tryptamine, 250mL of dichloromethane and 6.27g (55mmol) of trifluoroacetic acid are added dropwise at room temperature into a 500mL reaction bottle, after stirring and reacting for 8 hours, the reaction system is poured into a beaker filled with 250mL of ice water and 3g of sodium hydroxide, the mixture is stirred and separated, the aqueous phase is extracted for 2 times by 20mL of dichloromethane, the organic phases are combined, and the white solid product is obtained by silica gel column chromatography and elution of petroleum ether/dichloromethane. Yield: 92 percent;
step 2: synthesis of the Compound 1-phenyl-9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000171
adding 7.44g (30mmol) of the product 1-phenyl-2, 3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole in the step 1, 2.5g of 10% palladium/carbon and 250mL of xylene into a 500mL reaction bottle, stirring, heating, refluxing and reacting for 24 hours, cooling to room temperature, filtering, returning a filter cake into the reaction bottle, adding 200mL of tetrahydrofuran and 200mL of dichloromethane, stirring, heating, refluxing for 2 hours, cooling to room temperature, filtering, concentrating the filtrate under reduced pressure, adding 20mL of ethyl acetate, filtering, washing the filter cake with ethyl acetate, and drying to obtain an off-white solid. Yield: 65 percent;
and step 3: synthesis of the compound 9-phenyl-1-phenyl-9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000172
adding 7.35g (30mmol) of the product 1-phenyl-9H-pyrido [3,4-b ] indole in the step 2 and 50mL of dry dimethyl sulfoxide into a 250mL reaction bottle, cooling the mixture to 5 ℃ in an ice water bath, adding 2.4g (36mmol, 85%) of potassium hydroxide in batches, reacting the mixture for 1 hour under stirring at a constant temperature, adding 7.3g (36mmol) of iodobenzene, reacting the mixture for 1 hour under stirring at room temperature, heating the mixture to 85 ℃, reacting the mixture for 24 hours under stirring, cooling the mixture to the room temperature, pouring the reaction liquid into 200mL of ice water, extracting the mixture with ethyl acetate, separating an organic phase, concentrating the organic phase under reduced pressure to dryness, separating and purifying the residue by using a silica gel column, and eluting the residue with ethyl acetate/petroleum ether to obtain a yellow solid. Yield: 84%;
and 4, step 4: synthesis of compound IV:
Figure BDA0001496453450000173
5.0g (15.6mmol) of the product 9-phenyl-1-phenyl-9H-pyrido [3,4-b ] indole obtained in step 3, 90mL of ethylene glycol ethyl ether and 30mL of water are put into a 250mL reaction flask, 2.7g (7.6mmol) of iridium chloride is added, the mixture is heated and refluxed for 12 hours, cooled to room temperature, filtered, the filter cake is washed with water and ether, and dried in vacuum to obtain a red solid. Yield: 76 percent.
And 5: synthesis of Compound OR-1
Figure BDA0001496453450000174
Into a 250mL reaction flask, 5.0g (2.9mmol) of the product of step 4, formula IV, 722mg (7.2mmol) of acetylacetone, 20mL of acetonitrile and 20mL of chloroform were charged, 3.1g (29mmol) of anhydrous sodium carbonate was added, the mixture was refluxed at elevated temperature for 12 hours, cooled to room temperature, poured into 200mL of water, extracted with chloroform, dried under reduced pressure, concentrated to dryness, and separated and purified by silica gel column to obtain the product, formula OR-1, as a reddish brown solid.
The structure and performance detection results of the OR-1 compound are as follows:
(1)1H NMR(CDCl3300 MHz): see figure 1. As shown in FIG. 1, the structure of the reddish brown solid product is compound OR-1.
(2) Glass transition temperature Tg: 300 ℃ is adopted;
(3) ultraviolet absorption wavelength: 290.5nm, 370 nm;
(4) phosphorescence emission wavelength: 584 nm.
Example 2 synthesis of organic electroluminescent compound OR-10:
Figure BDA0001496453450000181
step 1: synthesis of compound 1- (2-thienyl) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole
Figure BDA0001496453450000182
Following the procedure of example 1, only benzaldehyde used in step 1) was replaced with 2-thiophenecarboxaldehyde to give the target compound 1- (2-thienyl) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole as a brown oil, yield: 94 percent;
step 2: synthesis of the compound 1- (2-thienyl) -9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000183
following the procedure of example 1, only 1-phenyl-2, 3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole used in step 2) was replaced with 1- (2-thienyl) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole to give the target compound 1- (2-thienyl) -9H-pyrido [3,4-b ] indole as yellow crystals, yield: 74 percent;
and step 3: synthesis of compound V:
Figure BDA0001496453450000184
following the procedure of example 1, only the 1-phenyl-9H-pyrido [3,4-b ] indole used in step 3) was replaced with 1- (2-thienyl) -9H-pyrido [3,4-b ] indole to give the title compound of formula V, yellow crystals, yield: 82%;
and 4, step 4: synthesis of Compound VI:
Figure BDA0001496453450000185
following the procedure of example 1, the 9-phenyl-1-phenyl-9H-pyrido [3,4-b ] indole used in step 4) was replaced with the product of step 3, formula V, to give the iridium bridged compound, formula VI, as a red brown solid powder in yield: 87 percent;
and 5: synthesis of Compound OR-10:
Figure BDA0001496453450000191
following the procedure of example 1, substituting formula IV for compound formula VI used in step 5) provided a compound of iridium complex formula OR-10 as a red solid in yield: 85 percent.
The structure and performance detection results of the product OR-10 compound are as follows:
(1)1H NMR(CDCl3300 MHz): δ 8.482-8.474(d,2H),8.154-8.135(d,2H),7.713-7.698(d,2H),7.488-7.184(m,15H),6.953-6.942(m,3H),6.039-5.988(m,2H),5.277(s,1H),1.863(s, 6H). As can be seen from the above, the structure of the red solid product is compound OR-10.
(2) Glass transition temperature Tg: 300 ℃ is adopted;
(3) ultraviolet absorption wavelength: 435nm, 502 nm;
(4) phosphorescence maximum emission wavelength: 618nm (see FIG. 2).
Example 3 synthesis of organic electroluminescent compound OR-20:
Figure BDA0001496453450000192
step 1: synthesis of the compound 1-phenyl-9- (2-thienyl) -9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000193
following the procedure of example 1, only iodobenzene used in step 3) was replaced with 2-iodothiophene to give the target compound 1-phenyl-9- (2-thienyl) -9H-pyrido [3,4-b ] indole as a yellow solid in yield: 94 percent;
step 2: synthesis of compound VII:
Figure BDA0001496453450000194
following the procedure of example 1, the 9-phenyl-1-phenyl-9H-pyrido [3,4-b ] indole used in step 4) was replaced with 1-phenyl-9- (2-thienyl) -9H-pyrido [3,4-b ] indole to give the iridium bridged compound formula VII, a reddish brown solid powder, yield: 85 percent;
and step 3: synthesis of Compound OR-20:
Figure BDA0001496453450000201
following the procedure of example 1, substituting formula IV used in step 5) with compound formula VII, an iridium compound of complex formula OR-20 was obtained as a brown solid in yield: 82 percent.
The structure and performance detection results of the product are as follows:
(1)1H NMR(CDCl3300 MHz): δ 8.484-8.476(d,2H),8.155-8.136(d,2H),7.901-7.836(m,4H),7.486-7.188(m,12H),6.955-6.940(m,4H),6.046-5.991(m,2H),5.275(s,1H),1.862(s, 6H). As can be seen from the above, the brown solid product has the structure of compound OR-20.
(2) Glass transition temperature Tg: 300 ℃ is adopted;
(3) ultraviolet absorption wavelength: 355nm, 375 nm;
(4) phosphorescence maximum emission wavelength: 582 nm.
Example 4 synthesis of organic electroluminescent compound OR-69:
Figure BDA0001496453450000202
step 1: synthesis of compound 1- (9, 9-dimethyl-9H-2-fluorenyl) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole:
Figure BDA0001496453450000203
following the procedure of example 1, only benzaldehyde used in step 1) was replaced with 9, 9-dimethyl-9H-fluorene-2-carbaldehyde to give the objective compound 1- (9, 9-dimethyl-9H-2-fluorenyl) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole as a white solid in yield: 88 percent;
step 2: synthesis of the compound 1- (9, 9-dimethyl-9H-2-fluorenyl) -9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000204
following the procedure of example 1, only 1-phenyl-2, 3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole used in step 2) was replaced with 1- (9, 9-dimethyl-9H-2-fluorenyl) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole to give the objective compound 1- (9, 9-dimethyl-9H-2-fluorenyl) -9H-pyrido [3,4-b ] indole as yellow crystals, yield: 85 percent;
and step 3: synthesis of the compound 1- (9, 9-dimethyl-9H-2-fluorenyl) -9- (3-pyridyl) -9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000205
following the procedure of example 1, only 1-phenyl-9H-pyrido [3,4-b ] indole used in step 3) was replaced with 1- (9, 9-dimethyl-9H-2-fluorenyl) -9H-pyrido [3,4-b ] indole while iodobenzene was replaced with 3-bromopyridine to give the objective compound 1- (9, 9-dimethyl-9H-2-fluorenyl) -9- (3-pyridyl) -9H-pyrido [3,4-b ] indole as yellow crystals in yield: 52 percent;
and 4, step 4: synthesis of compound IX:
Figure BDA0001496453450000211
following the procedure of example 1, only the 9-phenyl-1-phenyl-9H-pyrido [3,4-b ] indole used in step 4) was replaced with 1- (9, 9-dimethyl-9H-2-fluorenyl) -9- (3-pyridyl) -9H-pyrido [3,4-b ] indole to give iridium-bridged compound IX, brown particles, yield: 62 percent;
and 5: synthesis of Compound OR-69
Figure BDA0001496453450000212
Following the procedure of example 1, substituting formula IV used in step 5) with compound formula IX, an iridium compound of formula OR-69 was obtained as a brown solid in yield: 84 percent.
The structure and performance detection results of the product are as follows:
(1)1H NMR(CDCl3300 MHz): δ 8.693(s,2H),8.475-8.459(d,2H),8.178-8.163(d,2H),7.814-7.775(m,4H),7.427-7.373(m,6H),7.328-7.284(m,6H),7.246-7.201(m,6H),6.958-6.922(m,4H),5.196(s,1H),3.982(s,6H),1.787(s,6H),1.714(s, 6H). As can be seen from the above, the brown solid product has a correct structure and is compound OR-69.
(2) Glass transition temperature Tg: 300 ℃ is adopted;
(3) ultraviolet absorption wavelength: 395nm and 496 nm;
(4) phosphorescence emission wavelength: 612 nm.
Example 5 synthesis of organic electroluminescent compound OR-112:
Figure BDA0001496453450000213
step 1: synthesis of compound XI:
Figure BDA0001496453450000221
following the procedure of example 1, replacing only the 1-phenyl-9H-pyrido [3,4-b ] indole used in step 3) with 1- (2-thienyl) -9H-pyrido [3,4-b ] indole and the iodobenzene used with 2-bromotoluene, the title compound of formula XI was obtained in the form of yellow crystals, yield: 76%;
step 2: synthesis of compound XII:
Figure BDA0001496453450000222
into a 250mL reaction flask was charged 5.0g (15.6mmol) of the compound of formula XI, 90mL of ethylene glycol ethyl ether and 30mL of water, 5.5g (13.2mmol) of potassium tetrachloroplatinate was added, the mixture was heated under reflux for 12 hours, cooled to room temperature, filtered, the cake was washed with water, ether and dried under vacuum to give a red solid, yield: 83 percent;
and step 3: synthesis of Compound OR-112:
Figure BDA0001496453450000223
into a 250mL reaction flask, 5.0g (4.3mmol) of the product of step 2, formula XII, 1.1g (10.9mmol) of acetylacetone, 50mL of acetonitrile and 50mL of chloroform were charged, 4.6g (43.3mmol) of anhydrous sodium carbonate was added, the reaction was refluxed at elevated temperature for 12 hours, cooled to room temperature, poured into 200mL of water, extracted with chloroform, dried the organic phase, concentrated under reduced pressure to dryness, and separated and purified by silica gel column to obtain the product, compound of formula OR-112, as a red solid.
The structure and performance detection results of the product are as follows:
(1)1H NMR(CDCl3300 MHz): δ 8.482-8.474(d,2H),8.144-8.125(d,2H),7.478-7.439(m,4H),7.058-7.022(m,4H),5.215(s,1H),1.868(s,3H),1.774(s, 6H). As can be seen from the above, the reddish brown solid product has a correct structure and is the compound OR-112.
(2) Glass transition temperature Tg: 300 ℃ is adopted;
(3) ultraviolet absorption wavelength: 445nm, 508 nm;
(4) phosphorescence maximum emission wavelength: 622 nm.
Example 6 synthesis of organic electroluminescent compound OR-129(Z ═ 0):
Figure BDA0001496453450000224
step 1: synthesis of the compound 1- (4-dibenzo [ b, d ] furan) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole:
Figure BDA0001496453450000231
following the procedure of example 1, only benzaldehyde used in step 1) was replaced with dibenzo [ b, d ] furan-4-carbaldehyde to give the target compound 1- (4-dibenzo [ b, d ] furan) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole, white solid, yield: 85 percent;
step 2: synthesis of the compound 1- (4-dibenzo [ b, d ] furan) -9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000232
following the procedure of example 1, only 1-phenyl-2, 3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole used in step 2) was replaced with 1- (4-dibenzo [ b, d ] furan) -2,3,4, 9-tetrahydro-1H-piperidino [3,4-b ] indole to give the target compound 1- (4-dibenzo [ b, d ] furan) -9H-pyrido [3,4-b ] indole, yellow solid, yield: 79 percent;
and step 3: synthesis of the compound 1- (4-dibenzo [ b, d ] furan) -9-phenyl-9H-pyrido [3,4-b ] indole:
Figure BDA0001496453450000233
following the procedure of example 1, only 1-phenyl-9H-pyrido [3,4-b ] indole used in step 3) was replaced with 1- (4-dibenzo [ b, d ] furan) -9H-pyrido [3,4-b ] indole to give the target compound 1- (4-dibenzo [ b, d ] furan) -9-phenyl-9H-pyrido [3,4-b ] indole as a yellow solid in yield: 74 percent;
and 4, step 4: synthesis of compound XIII:
Figure BDA0001496453450000234
following the procedure of example 5, replacing only compound XI used in step 2) with the product of step 3, the title compound, formula XIII, was obtained as a red solid in yield: 62 percent;
and 5: synthesis of compound OR-129(Z ═ O):
Figure BDA0001496453450000241
following the procedure of example 5, substituting only compound XII used in step 3) with compound XIII affords the target compound of formula OR-129(Z ═ O), red solid, yield: 58 percent.
The structure and performance detection results of the product are as follows:
(1)1H NMR(CDCl3300 MHz): δ 8.473-8.455(d,2H),8.246-8.227(d,2H),7.901-7.883(m,2H),7.474-7.455(m,3H),7.325-7.258(m,4H),7.053-7.016(m,4H),5.247(s,1H),1.864(s, 6H). As can be seen from the above, the structure of the reddish brown solid product is compound OR-129;
(2) glass transition temperature Tg: 300 ℃ is adopted;
(3) ultraviolet absorption wavelength: 446nm, 515 nm;
(4) phosphorescence maximum emission wavelength: 626 nm.
The organic electroluminescent compound shown in the formula I has high glass transition temperature and good luminous capacity, so that the organic electroluminescent compound has good application prospect in the field of OLEDs. On the basis of the preparation processes of the six embodiments, the quality of the obtained OLED material is not affected by enlarging or reducing the reactant dosage in the same ratio.
EXAMPLE 7 preparation of electroluminescent device OD-1
1) Carrying out ultrasonic treatment on the glass substrate coated with the ITO conductive layer in a cleaning agent for 30 minutes, washing the glass substrate in deionized water, carrying out ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baking the glass substrate in a clean environment until the glass substrate is completely dried, irradiating the glass substrate for 10 minutes by using an ultraviolet light cleaning machine, and bombarding the surface by using low-energy cation beams;
2) placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, continuously evaporating BNP as a hole injection layer and TAPC as a hole transport layer on the anode layer film respectively, and evaporatingThe plating rate is 0.1nm/s, and the thickness of each evaporation film is 10 nm;
wherein the structural formulas of BNP and TAPC are as follows:
Figure BDA0001496453450000242
3) continuously evaporating a layer of the mixture consisting of the organic electroluminescent compound OR-10 shown in the formula I obtained in the example 2 and the phosphorescent host material TZPPI on the hole transport layer to be used as an organic light-emitting layer of the device, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 80 nm; wherein, the compound OR-10 shown in the formula I accounts for 2 percent of the mass of the TZPPI;
wherein, the structural formula of TZPPI is as follows:
Figure BDA0001496453450000251
4) continuously evaporating a TPBI material layer on the organic light-emitting layer to serve as an electron transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 50 nm;
wherein the structural formula of TPBI is as follows:
Figure BDA0001496453450000252
5) and sequentially evaporating a magnesium/silver alloy layer on the electron transport layer to be used as a cathode layer of the device, wherein the evaporation rate of the magnesium/silver alloy layer is 2.0-3.0nm/s, the evaporation film thickness is 100nm, and the mass ratio of magnesium to silver is 1:9, so that the device OD-1 provided by the invention is obtained.
EXAMPLE 8 preparation of electroluminescent devices OD-2 and OD-3
By following the same procedure as in example 7, replacing OR-10 used in step 3) with the compound OR-50 represented by formula I, an electroluminescent device OD-2 provided by the present invention was obtained.
The same procedure as in example 7 was followed to replace OR-10 used in step 3) with OR-112, a compound of formula I, to give an electroluminescent device OD-3 as provided by the present invention.
COMPARATIVE EXAMPLE 1 preparation of device OD-4
Following the same procedure as in example 7, only OR-10 used in step 3) was replaced with Ir (dpm) PQ2And obtaining the device OD-4.
Wherein Ir (dpm) PQ2The structural formula of (A) is as follows:
Figure BDA0001496453450000253
the results of performance measurements of the resulting devices OD-1 to OD-4 are shown in Table 1 below.
TABLE 1 Performance test results of OD-1 to OD-4
Figure BDA0001496453450000254
Figure BDA0001496453450000261
It is obvious from the above that the organic light emitting device made of the organic electroluminescent compound of the present invention has high power efficiency, low lighting voltage and light color in deep red light region.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. An organic electroluminescent compound, characterized in that the structural formula is shown as formula I below:
Figure FDA0003006894210000011
wherein:
Ar1any one selected from the following groups:
Figure FDA0003006894210000012
Ar2any one selected from the following groups:
Figure FDA0003006894210000013
R1、R2、R3、R4all are hydrogen;
R5、R8each independently selected from any one of H and alkyl with 1-15 carbon atoms in total;
m is selected from Ir or Pt;
l is any one of acetylacetone group, acetoacetyl group with branch chain with 5-25 carbon atoms in total, and straight chain acetoacetyl group with 5-25 carbon atoms in total;
x is 1 or 2 or 3;
y is 0 or 1 or 2 or 3;
Figure FDA0003006894210000014
represents a substitution bit;
represents a coordinate bond.
2. The organic electroluminescent compound according to claim 1, wherein the alkyl groups having a total number of carbon atoms of 1 to 15 are selected from one of C2 to C15 alkyl groups.
3. The organic electroluminescent compound according to claim 1, wherein the structural formula of the organic electroluminescent compound of formula I is specifically represented by any one of the following formulas:
Figure FDA0003006894210000015
Figure FDA0003006894210000021
wherein: z is selected from O or S.
4. A method for producing an organic electroluminescent compound according to any one of claims 1 to 3, comprising the steps of:
has a structural formula of
Figure FDA0003006894210000022
The compound and the ligand L are subjected to coordination reaction in the presence of alkali to obtain an organic electroluminescent compound shown in a formula I;
wherein:
the radicals are as defined in claim 1.
5. The method of claim 4, wherein the base is selected from sodium carbonate or potassium carbonate.
6. The method as claimed in claim 4, wherein the coordination reaction is carried out under an inert atmosphere at a temperature of 150 ℃ to 200 ℃ for 8 to 24 hours.
7. Use of the organic electroluminescent compounds as claimed in any of claims 1 to 3 for the preparation of electroluminescent devices.
8. Use according to claim 7, wherein the electroluminescent device is an organic light-emitting diode.
9. An electroluminescent device comprising the organic electroluminescent compound as claimed in any one of claims 1 to 3.
10. The electroluminescent device according to claim 9, wherein the organic electroluminescent compound is a material constituting an organic light-emitting layer of the electroluminescent device.
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