CN109942637B - Metal complex and organic electroluminescent device - Google Patents

Metal complex and organic electroluminescent device Download PDF

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CN109942637B
CN109942637B CN201910261031.5A CN201910261031A CN109942637B CN 109942637 B CN109942637 B CN 109942637B CN 201910261031 A CN201910261031 A CN 201910261031A CN 109942637 B CN109942637 B CN 109942637B
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曹建华
郭剑
邵哲
纪秦思
贾敏慧
何伟壮
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Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
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Abstract

The invention discloses a metal complex and an organic electroluminescent device containing the same. The molecular formula of the metal complex of the invention is M (L)A)x(LB)y(ii) a The metal complex electroluminescent device has high luminous efficiency, good thermal stability, easy preparation and purification, and is an ideal choice as the luminescent material of the organic electroluminescent device.

Description

Metal complex and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic electroluminescence. And more particularly, to a metal complex for organic electroluminescence, an organic 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, fast response speed, low driving voltage, low power consumption, bright color, high contrast, simple process, good temperature characteristic, soft display realization and the like, and can be widely applied to flat panel displays and surface light sources, thereby being widely researched, developed and used.
At present, red and green phosphorescent materials still have the problems of low luminous quantum efficiency and poor color purity. The main reason for this is that phosphorescence comes from transition between energy levels with narrow energy gaps, while heavy metal complexes with narrow forbidden bands have certain difficulty in ligand design, and secondly, the system of the phosphorescent material has strong pi-pi bond interaction, and the ligands have strong charge transfer characteristics, so that more radiationless relaxation channels exist in the narrow band gaps, the quenching of the phosphor is accelerated, and the quantum yield and the molecular stability of the phosphorescent system are reduced. Therefore, designing and synthesizing red and green phosphorescent materials with excellent comprehensive performance becomes an important subject of organic electroluminescent material research.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides a metal complex which emits green light and has high luminous efficiency.
Specifically, the present invention includes the following:
the invention provides a metal complex, the molecular formula of which is M (L)A)x(LB)y，
Wherein M represents a metal element having an atomic weight of more than 40;
x represents an integer of 1, 2 or 3; y represents an integer of 0, 1 or 2; and x + y is equal to the oxidation state of metal M;
LAcomprises the following steps:
Figure BDA0002015270140000021
formula LAIn (1),
A1、A2、A3、A4each independently selected from carbon or nitrogen;
R1、R2、R3、R4、R5each independently selected from a hydrogen atom,Deuterium atom, halogen atom, alkyl group, cycloalkyl group, heteroalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, silane group, alkenyl group, cycloalkenyl group, heteroalkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, carbonyl group, carboxylic acid group, ester group, nitrile group, isonitrile group, sulfonyl group, sulfinyl group, sulfone group, phosphorus group; r1、R2、R3、R4、R5Wherein any adjacent substituents are optionally joined or fused to form a five-membered ring, a six-membered ring, or a seven-or more-membered ring;
LBcomprises the following steps:
Figure BDA0002015270140000022
formula LBIn (1),
A5is carbon or nitrogen;
R6、R7each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, a silyl group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfonyl group, a sulfinyl group, a sulfone group, a phosphorus group; r6、R7Wherein any adjacent substituents are optionally joined or fused to form a five-membered ring, a six-membered ring, or a seven-or more-membered ring;
ring C, ring D are each independently selected from a five-membered carbocyclic ring, a six-membered carbocyclic ring, or a heterocyclic ring.
In certain embodiments, the aforementioned metal M is selected from Ir or Pt.
In certain embodiments, the foregoing metal complexes have the formula Ir (LA) (LB)2、Ir(LA)2(LB) or Ir (LA)3。
In certain embodiments, the foregoing structural formula LASelected from the group consisting of the following structural formulas:
Figure BDA0002015270140000031
wherein R is1、R2、R3、R4、R5Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, a silyl group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfonyl group, a sulfinyl group, a sulfone group, a phosphorus group; r1、R2、R3、R4、R5Any of which are optionally joined or fused to form a five-membered ring, a six-membered ring, or a seven-or more-membered ring.
In certain embodiments, the aforementioned structural formula LAI is selected from the group consisting of the structures shown in LA 1-LA 330 below:
the structural formula of the formula LAI is selected from the group consisting of structures represented by LA1 to LA330 described below.
Figure BDA0002015270140000032
Figure BDA0002015270140000041
Figure BDA0002015270140000051
Figure BDA0002015270140000061
Figure BDA0002015270140000071
Figure BDA0002015270140000081
Figure BDA0002015270140000091
Figure BDA0002015270140000101
Figure BDA0002015270140000111
Figure BDA0002015270140000121
Figure BDA0002015270140000131
The structural formula of the formula LAII is selected from the group consisting of structures represented by LA331 to LA535 described below.
Figure BDA0002015270140000132
Figure BDA0002015270140000141
Figure BDA0002015270140000151
Figure BDA0002015270140000161
Figure BDA0002015270140000171
Figure BDA0002015270140000181
Figure BDA0002015270140000191
The structural formula of formula laii is selected from the group consisting of structures represented by LA536 to LA685 described below.
Figure BDA0002015270140000192
Figure BDA0002015270140000201
Figure BDA0002015270140000211
Figure BDA0002015270140000221
Figure BDA0002015270140000231
The structural formula of the formula LAIV is selected from the group consisting of structures represented by LA686 to LA805 described below.
Figure BDA0002015270140000232
Figure BDA0002015270140000241
Figure BDA0002015270140000251
Figure BDA0002015270140000261
The structural formula of the formula LAV is selected from the group consisting of structures represented by LA806 to LA930 described below.
Figure BDA0002015270140000262
Figure BDA0002015270140000271
Figure BDA0002015270140000281
Figure BDA0002015270140000291
Figure BDA0002015270140000301
The structural formula of formula LAVI is selected from the group consisting of structures represented by LA931 to LA1065 described below.
Figure BDA0002015270140000302
Figure BDA0002015270140000311
Figure BDA0002015270140000321
Figure BDA0002015270140000331
The structural formula of the formula LAVII is selected from the group consisting of structures shown in LA 1066-LA 1185 below.
Figure BDA0002015270140000341
Figure BDA0002015270140000351
Figure BDA0002015270140000361
Figure BDA0002015270140000371
The structural formula of the formula LAVIII is selected from the group consisting of structures represented by LA 1186-LA 1250 shown below.
Figure BDA0002015270140000372
Figure BDA0002015270140000381
Figure BDA0002015270140000391
In certain embodiments, the aforementioned LBSelected from the group consisting of the structures shown in LBI, LBII, LBIII, LBIV, LBV, LBVI, LBVII, LBVIII, LBIX, LBX, LBXI below.
Figure BDA0002015270140000392
Figure BDA0002015270140000401
X1～X17Each independently selected from carbon or nitrogen;
x is selected from the group consisting of: -B (R ') -, -N (R') -, -P (R ') -, -O-, -S-, -Se-, -C (═ O) -, -S (O') -)2)-、-C(R’R”)-、-Si(R’R”)-、-Ge(R’R”)-；
R’、R”、Ra、Rb、Rc、RdEach independently selected from the group consisting of: hydrogen atom, deuterium atom, halogen atom, alkyl group, cycloalkyl group, heteroalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, silyl group, alkenyl group, cycloalkenyl group, isoalkenyl group, alkynyl group, aryl group, heterocyclic aryl group, aliphatic hydrocarbon group containing nitrogen, germanium, oxygen or sulfur, phosphine group, phosphino group;
Ra、Rb、Rc、Rdany two adjacent substituents in (a) are optionally fused or joined to form a five-membered ring, a six-membered ring or to form a multidentate ligand.
In certain embodiments, the foregoing structural formula LBSelected from the group consisting of the structures shown as LB 1-LB 236:
Figure BDA0002015270140000402
Figure BDA0002015270140000411
Figure BDA0002015270140000421
Figure BDA0002015270140000431
Figure BDA0002015270140000441
Figure BDA0002015270140000451
Figure BDA0002015270140000461
Figure BDA0002015270140000471
Figure BDA0002015270140000481
in certain embodiments, the foregoing metal complexes have the formula Ir (LAi) or (LBj)2、Ir(LAi)2(LBj) or Ir (LAi)3Wherein LAi is selected from the group consisting of the structures shown in LA 1-LA 1250 previously described; LBj is selected from the group consisting of structures LB 1-LB 236.
Another aspect of the present invention provides an organic electroluminescent material comprising one or more metal complexes of the present invention.
Specifically, the organic electroluminescent material of the present invention may be formed of only one or more of the metal complexes of the present invention, or may contain other materials than the metal complexes of the present invention.
By containing the metal complex of the present invention in the organic electroluminescent material of the present invention, an organic electroluminescent material having a high luminous efficiency and a long life of a deep red primary emitter/dopant system suitable for an organic electroluminescent device can be obtained.
Another aspect of the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers comprising the metal complex of the present invention interposed between the first electrode and the second electrode, the organic layers being selected from the group consisting of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer, and an organic light emitting layer.
In some embodiments, the organic layer is an organic light-emitting layer comprising a host material and the metal complex of the present invention doped in the host material,
in certain embodiments, the aforementioned host material is selected from the group consisting of:
Figure BDA0002015270140000491
in another aspect of the present invention, there is also provided an electronic device comprising the organic electroluminescent device of the present invention.
The invention has the advantages of
The metal complex is an electrophosphorescent luminescent material of phenanthrene or azaphenanthrene metal complex with a fused ring structure. The metal complex disclosed by the invention is green in electroluminescence and high in luminous efficiency. In addition, the metal complex has good thermal stability, so that the metal complex is easy to prepare, sublimate and purify and has very wide market prospect.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a schematic structural diagram of an OLED device in example 14 of the present invention, wherein 1 represents a substrate, 2 represents an anode layer, 3 represents a hole injection layer, 4 represents a hole transport layer, 5 represents an organic light emitting layer, 6 represents an electron transport layer, and 7 represents a cathode layer.
FIG. 2 shows a molecular formula of Ir (LA143)2Phosphorescence spectrum of the compound of (LB 82).
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. 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.
[ Metal complexes ]
The metal complex is prepared by taking modified aryl ketone as a raw material under a proper condition and carrying out preparation processes such as cyclization, coordination and the like. The simple organic preparation involved in the preparation of the metal complexes of the present invention is not described in detail herein.
[ organic electroluminescent Material ]
The organic electroluminescent material of the present invention contains one or more of the metal complexes of the present invention. The organic electroluminescent material of the present invention may be formed of only one or more of the metal complexes of the present invention, or may contain other materials than the metal complexes of the present invention.
The metal complexes of the invention are also included within the scope of the invention, either as luminescent materials alone or as doping materials in luminescent materials.
By including the metal complex in the organic electroluminescent material of the present invention, an organic electroluminescent material having good stability and excellent light-emitting properties suitable for an organic electroluminescent device can be obtained.
[ organic electroluminescent device ]
The organic electroluminescent device of the present invention comprises a first electrode, a second electrode and at least one organic layer containing the metal complex of the present invention disposed between the first electrode and the second electrode. The organic layer is a layer selected from the group consisting of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer, and an organic light emitting layer. The aforementioned organic layer may optionally contain other materials for forming the layer in addition to the metal complex of the present invention.
For example, when the metal complex of the present invention is contained in the organic light-emitting layer of the organic electroluminescent device of the present invention, the organic light-emitting layer may contain a commonly added substance such as a known dopant and a host light-emitting substance.
Other configurations of the organic electroluminescent element are not particularly limited. In one embodiment of the organic light-emitting device, for example, in the case where the organic layer is an organic light-emitting layer, one or more layers selected from an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, and a hole injection layer may be provided between the first electrode and the second electrode.
In one embodiment of the organic electroluminescent device, the organic light-emitting layer may comprise, for example, a material selected from the group consisting of naphthalene, anthracene, pyrene, perylene, phenanthrene, fluoranthene, perylene, phenanthrene, perylene, etc., as a primary light-emitting body,
Figure BDA0002015270140000511
One or more of benzanthracene, pentacene, carbazole, benzofuran, benzothiophene, indole, and derivatives thereof, and one or more of the metal complexes of the present invention as a dopant.
In the organic electroluminescent device of the present invention, the metal complex of the present invention contained in the organic light-emitting layer may be a material which emits light when doped in a host material or may be a material which emits light when undoped. Specifically, the organic light-emitting layer can be further doped with a phosphorescent dye by using a small molecule material as a host material. The material of the organic light emitting layer may include the metal complex of the present invention as a phosphorescent dopant material to emit light in a corresponding host material.
In the organic electroluminescent device of the present invention, the constitution of the layer other than the layer containing the metal complex of the present invention is not limited at all, and a person skilled in the art can determine the constitution of other layers of the organic electroluminescent device as necessary based on the common knowledge in the art.
A specific example of the organic electroluminescent device according to the present invention will be described with reference to fig. 1. Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present invention. In fig. 1, an anode layer 2, a hole injection layer 3, a hole transport layer 4, an organic light emitting layer 5, an electron transport layer 6, and a cathode layer 7 are provided in this order on a substrate 1. The organic light-emitting layer 5 contains the metal complex of the present invention. When the organic electroluminescent device of the present invention is connected to an external power source and a voltage is applied, the metal complex in the organic light emitting layer 5 generates electroluminescence.
The method for manufacturing the organic electroluminescent device of the present invention includes the following methods, but is not limited thereto, and those skilled in the art can variously change the method according to the general knowledge in the art. The preparation method comprises the following steps:
a cleaning procedure: cleaning a glass substrate with ITO by using a cleaning agent, deionized water, an organic solvent and the like, and using the ITO on the glass substrate as an anode layer;
step of forming a hole injection layer: forming a hole injection layer on the substrate by evaporating a hole injection layer forming material on the ITO as the anode layer by vacuum evaporation;
step (2) of forming a hole transport layer: forming a hole transport layer on the hole injection layer by vacuum evaporation;
a step of forming an organic light-emitting layer: forming an organic light-emitting layer containing the metal complex of the present invention on the hole transport layer by vacuum evaporation of an organic light-emitting layer-forming material containing the metal complex of the present invention on the hole transport layer;
a step of forming an electron transport layer: forming an electron transport layer on the organic light emitting layer by vacuum vapor depositing an electron transport layer forming material on the organic light emitting layer;
a step of forming a cathode layer: a cathode forming material is vapor-deposited, sputtered, or spin-coated on the electron transporting layer to form a cathode layer.
[ electronic apparatus ]
The electronic device of the present invention contains the organic electroluminescent device of the present invention. Other configurations of the electronic device of the present invention are not particularly limited.
Examples
In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are available from published commercial sources unless otherwise specified, and the percentages are by mass unless otherwise specified.
The following abbreviations are used in the examples of the present invention:
TABLE 1 abbreviations and full names
Abbreviations Full scale
THF Tetrahydrofuran (THF)
n-BuLi Lithium ortho-radical
NBS N-bromosuccinimide
(PinB)2 Biboric acid pinacol ester
Pd(PPh3)4 Tetrakis (triphenylphosphine) palladium
dppf
1,1' -bis (diphenylphosphino) ferrocene
[ PREPARATION OF LIGANDS ]
Example 1
Preparation of compound LA 2:
the preparation method of the ligand LA2 comprises the following steps:
the first step is as follows: preparation of Compound Int-1
Figure BDA0002015270140000531
61.5g (0.11mol) of 2-iodobenzyltriphenylphosphonium salt are dispersed in 350mL of anhydrous THF, the temperature is reduced to 0 ℃ by an ice salt bath under the protection of nitrogen, 14.8g (0.13mmol) of potassium tert-butoxide is added in portions, 20.0g (0.1mol) of 2-bromo-5-methylbenzaldehyde is added dropwise after stirring reaction for 30 minutes, after the addition is finished, stirring reaction is carried out at constant temperature for 1 hour, the reaction is carried out at room temperature for 24 hours, 150mL of saturated aqueous ammonium chloride solution is added, extraction is carried out with ethyl acetate, the organic phase is dried with anhydrous sodium sulfate, filtration and concentration under reduced pressure is carried out, and separation and purification are carried out by a silica gel column, so that 36.7g of yellow oily substance is obtained as a cis/trans mixture, and the yield: 92 percent.
The second step is that: preparation of Compound Int-2
Figure BDA0002015270140000532
Dissolving 35.0g (87.7mmol) of the intermediate Int-1 prepared in the first step in 250mL of toluene, adding 31.5g (0.10mol) of tri-n-butyltin hydride, adding 2.9g (17.6mmol) of azobisisobutyronitrile, heating under the protection of nitrogen, refluxing and stirring for reaction for 12 hours, adding 5.2g (17.6mmol) of tri-n-butyltin hydride and 0.6g (3.5mmol) of azobisisobutyronitrile, continuing refluxing and stirring for reaction for 12 hours, cooling to room temperature, concentrating under reduced pressure, dissolving with dichloromethane, washing with water and saturated salt water, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, separating and purifying with a silica gel column to obtain 20.6g of white solid, wherein the yield is as follows: 87 percent.
The third step: preparation of Compound Int-3
Figure BDA0002015270140000533
Dissolving 20.0g (73.8mmol) of the intermediate Int-2 prepared in the second step in 150mL of dry THF, cooling to-78 ℃ with liquid nitrogen under the protection of nitrogen, dropwise adding 35.5mL of 2.5M N-butyllithium N-hexane solution, stirring for reaction for 30 minutes, dropwise adding 11.5g (0.11mol) of trimethyl borate in dry THF solution, heating to room temperature, stirring for reaction for 1 hour, adding 50mL of 3N diluted hydrochloric acid, stirring for reaction for 30 minutes, extracting with ethyl acetate, drying the organic phase, filtering, concentrating the filtrate under reduced pressure, adding petroleum ether for dispersion, filtering to obtain 12.9g of Int-3, a white solid, and the yield: 74 percent.
The fourth step: preparation of compound LA2
Figure BDA0002015270140000541
Under nitrogen, 10.0g (42.3mmol) of Int-3 prepared in the third step, 6.6g (42.3mmol) of 2-bromopyridine, 9.0g (84.9mmol) of anhydrous sodium carbonate were mixed, and 15.0mg of Pd (PPh) was added3)4The catalyst and 100mL of toluene, 50mL of ethanol and 20mL of water were heated to reflux, stirred and reacted for 12 hours, cooled to room temperature, diluted with 50mL of water, extracted with ethyl acetate, the organic phase was collected, dried, filtered, the filtrate was concentrated to dryness under reduced pressure, and separated and purified by a silica gel column to obtain 9.8g of a compound of formula LA2 as a yellow solid.
Example 2
Preparation of compound LA 143:
5.0g (18.5mmol) of LA2 was put into a single-neck reaction flask, 20mL of deuterated ethanol was added, 6.4g (93.0mmol) of sodium ethoxide was added, the mixture was refluxed for 48 hours at an elevated temperature, cooled to room temperature, concentrated to dryness under reduced pressure, and separated and purified by a silica gel column to obtain 4.8g of compound LA143 as a yellow solid.
Example 3
Preparation of compounds LA1, LA3 to LA330 referring to the preparation methods of example 1 and example 2, 1-carbonyl naphthalene with different substituents was substituted for 1-acetyl naphthalene in the first step of example 1, and 2-bromopyridine or 2-bromopyridine with different substituents was substituted for 2-bromopyridine in the fourth step of example 1, to prepare LA1, LA3 to LA330 in ligand LA.
Example 4
Preparation of compound LA 331:
the preparation method of the ligand LA331 comprises the following steps:
the first step is as follows: preparation of Compound Int-4
Figure BDA0002015270140000542
10.0g (55.8mmol) of benzo [ h ] quinoline and 20.0g (0.11mol) of NBS are dispersed in 100mL of N, N-dimethylacetamide, 1.7g (2.7mmol) of dichloro (p-methylisopropylphenyl) ruthenium (II) dimer catalyst are added, the reaction is stirred at 100 ℃ for 48 hours, the mixture is cooled to room temperature, 200mL of water is added for dilution, extraction is carried out with ethyl acetate, the organic phase is collected, dried, filtered, the filtrate is concentrated under reduced pressure and purified by silica gel column separation, and 10.9g of intermediate Int-4 is obtained as a yellow oil.
The second step is that: preparation of Compound Int-5
Figure BDA0002015270140000551
Referring to the preparation process of the third step of example 1, intermediate Int-5, a yellow powdery solid, was prepared by substituting intermediate Int-4 for Int-2 of the third step of example 1.
The third step: preparation of compound LA331
Figure BDA0002015270140000552
Referring to the fourth step of the procedure for the preparation of example 1, compound LA331, a yellow solid, was prepared by substituting intermediate Int-5 for Int-3 of the fourth step of example 1.
Example 5
Preparation of Compounds LA332 to LA535 LA332 to LA535 in ligand LA was prepared by substituting benzo [ h ] quinoline with a different substituent for benzo [ h ] quinoline in the first step of example 4 and substituting 2-bromopyridine or 2-bromopyridine with a different substituent for 2-bromopyridine in the third step of example 4, according to the preparation method of example 4.
Example 6
Preparation of compound LA 536:
a method for preparing ligand LA536, comprising the steps of:
the first step is as follows: preparation of Compound Int-6
Figure BDA0002015270140000561
Under nitrogen, 10.0g (58.1mmol) of 3-bromo-4-methylpyridine, 11.8g (63.9mmol) of 3-chloro-2-formylphenylboronic acid, 12.3g (0.11mol) of anhydrous sodium carbonate were mixed, and 3.4g of Pd (PPh)3)4The catalyst, 60mL of toluene, 30mL of methanol and 30mL of water were heated to 90 ℃ and stirred for reaction for 15 hours, the reaction mixture was cooled to room temperature, 50mL of water was added for dilution, extraction was performed with ethyl acetate, the organic phase was collected, dried, filtered, the filtrate was concentrated under reduced pressure and dried, and the resulting product was separated and purified by a silica gel column to obtain 11.8g of intermediate Int-6, a yellow solid.
The second step is that: preparation of Compound Int-7
Figure BDA0002015270140000562
Under the protection of nitrogen, 11.0g (47.4mmol) of the intermediate Int-6 prepared in the first step is dissolved in 150mL of DMF, 10.6g (95.0mmol) of potassium tert-butoxide is added in portions, the reaction is stirred at room temperature for 12 hours, the reaction solution is poured into 550mL of water and extracted with dichloromethane, the organic phase is dried over anhydrous sodium sulfate, filtered, concentrated to dryness under reduced pressure and separated and purified by a silica gel column to obtain 8.3g of the compound Int-7 as a white solid.
The third step: preparation of Compound Int-8
Figure BDA0002015270140000563
Referring to the preparation process of the third step of example 1, intermediate Int-8, a white solid, was prepared by substituting intermediate Int-7 for Int-2 of the third step of example 1.
The fourth step: preparation of compound LA536
Figure BDA0002015270140000564
Referring to the fourth step of the procedure for the preparation of example 1, compound LA536, a yellow solid, was prepared by substituting intermediate Int-8 for Int-3 of the fourth step of example 1.
Example 7
Preparation of Compounds LA537 to LA1250 referring to the preparation method of example 6, bromomethylpyridine having different substituents was substituted for 3-bromo-4-methylpyridine in the first step of example 6, and 2-bromopyridine having different substituents was substituted for 2-bromopyridine in the fourth step of example 6, to prepare LA537 to LA1250 in ligand LA.
Example 8
Metal complex Ir (LA2)2Preparation of (LB 77):
metal complex Ir (LA2)2The preparation method of (LB77) comprises the following steps:
the first step is as follows: preparation of Compound Int-9
Figure BDA0002015270140000571
5.0g of the compound LA2 and 2.5g of IrCl3·3H2O is dispersed in 150mL of ethylene glycol ethyl ether and 50mL of water, the mixture is heated and refluxed for reaction for 24 hours under the protection of nitrogen, the mixture is cooled to room temperature and filtered, and a filter cake is washed by water and methanol and is dried in vacuum to obtain 5.3g of compound Int-9 which is yellow solid.
The second step is that: preparation of Compound Int-10
Figure BDA0002015270140000572
5.3g of the compound Int-9 prepared in the above step was dissolved in 200mL of dichloromethane, and 3.6g of silver trifluoromethanesulfonate was added under nitrogen protection, and then 20mL of methanol was added, and the mixture was stirred at room temperature for 12 hours, and then filtered, and the filtrate was concentrated under reduced pressure to dryness to obtain 6.2g of the compound Int-10 as a yellow solid.
The third step: compound Ir (LA2)2Preparation of (LB77)
Figure BDA0002015270140000573
Dispersing 6.0g of compound Int-10 prepared in the second step and 2.2g of 2-phenylpyridine in 100mL of ethanol, heating and refluxing for reaction for 12 hours under the protection of nitrogen, cooling to room temperature, concentrating under reduced pressure to dryness, adding 100mL of petroleum ether for dispersion, filtering, and separating and purifying a filter cake by using a silica gel column to obtain 2.5g of compound Ir (LA2)2(LB77), yellow solid.
Example 9
The compound molecular formula Ir (LA143) (LB82)2The preparation of (1):
metal complex Ir (LA143) (LB82)2The preparation method comprises the following steps:
the first step is as follows: preparation of Compound Int-11
Figure BDA0002015270140000581
10.0g of the compound LB82 and 7.4g of IrCl3·3H2O is dispersed in 210mL of ethylene glycol ethyl ether and 70mL of water, the mixture is heated and refluxed for reaction for 24 hours under the protection of nitrogen, the mixture is cooled to room temperature and filtered, and a filter cake is washed by water and methanol and is dried in vacuum to obtain 12.5g of compound Int-11 which is yellow solid.
The second step is that: preparation of Compound Int-12
Figure BDA0002015270140000582
12.5g of the compound Int-11 prepared in the first step is dissolved in 500mL of dichloromethane, 5.5g of silver trifluoromethanesulfonate is added under the protection of nitrogen, 25mL of methanol is added, the mixture is stirred and reacted at room temperature for 12 hours, the reaction solution is filtered, and the filtrate is concentrated under reduced pressure to dryness to obtain 15.6g of the compound Int-12 as a yellow solid.
The third step: compound Ir (LA143) (LB82)2Preparation of
Figure BDA0002015270140000583
Dispersing 10.0g of the compound Int-12 prepared in the second step and 8.3g of LA143 in 150mL of ethanol, heating and refluxing for reaction for 12 hours under the protection of nitrogen, cooling to room temperature, concentrating under reduced pressure to dryness, adding 100mL of petroleum ether for dispersion, filtering, separating and purifying a filter cake by a silica gel column, washing with methanol, and drying to obtain 6.4g of compound Ir (LA143) (LB82)2Orange yellow solid.
Example 10
With reference to the preparation of example 8, the compounds of the invention were prepared: ir (LA)q)2(LBw) Q is an integer of 1 to 1250, and w is an integer of 1 to 236.
Example 11
With reference to the preparation of example 9, the compounds of the invention were prepared: ir (LA)q)(LBw)2Q is an integer of 1 to 1250, and w is an integer of 1 to 236.
Example 12
Compound formula Ir (LA471)3The preparation of (1):
metal complex Ir (LA471)3The preparation method comprises the following steps:
the first step is as follows: preparation of Compound Int-13
Figure BDA0002015270140000591
5.0g of the compound LA471 and 2.5g of IrCl3·3H2O is dispersed in90ml of ethylene glycol ethyl ether and 30ml of water are heated and refluxed for reaction for 24 hours under the protection of nitrogen, cooled to room temperature, filtered, and the filter cake is washed by water and ethanol and dried in vacuum to obtain 5.0g of compound Int-13 as yellow solid.
The second step is that: preparation of Compound Int-14
Figure BDA0002015270140000592
5.0g of the compound Int-13 prepared in the first step was dissolved in 600mL of dichloromethane, and under nitrogen protection, a solution of 1.7g of silver trifluoromethanesulfonate in 200mL of isopropanol was added, the reaction was stirred at room temperature for 24 hours, and the reaction solution was filtered, and the filtrate was concentrated under reduced pressure to dryness to obtain 6.0g of the compound Int-14 as a yellow solid.
The third step: compound Ir (LA471)3Preparation of
Figure BDA0002015270140000601
Dispersing 6.0g of the compound Int-14 prepared in the second step and 8.3g of LA471 in 150mL of ethanol, heating and refluxing for reaction for 24 hours under the protection of nitrogen, cooling to room temperature, filtering, washing a filter cake with ethanol, separating and purifying by a silica gel column, washing with petroleum ether, and drying to obtain 4.3g of compound Ir (LA471)3Orange solid.
Example 13
With reference to the preparation of example 12, the compounds of the invention were prepared: ir (LA)q)3And q is an integer of 1 to 1250.
Example 14
The OLED device shown in fig. 1 is prepared by the following steps, which include a substrate 1, an anode layer 2 disposed on the substrate 1, a hole injection layer 3 disposed on the anode layer 2, a hole transport layer 4 disposed on the hole injection layer 3, 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 the OLED device comprises the following steps:
1) the glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, washed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked to be completely dry in a clean environment, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the processed ITO glass substrate in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, continuously and respectively evaporating a compound HT01 as a hole injection layer on the ITO as the anode layer film, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm; continuously evaporating NPD on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
3) continuously evaporating a layer of the metal complex and H1+ H2 on the hole transport layer to be used as a luminescent layer of the device, wherein H1+ H2 is a mixed host material (the mixing ratio of H1 to H2 is 1:1) and the metal complex is a doping material, the evaporation rate ratio of the doping material to H1+ H2 is 1:100, the doping concentration of the metal complex is 1-10%, the total evaporation rate is 0.1nm/s, and the evaporation film thickness is 20 nm;
4) continuously evaporating a layer of LiQ material on the luminous layer to be used as an electron transmission layer of the device, wherein the plating rate is 0.1nm/s, and the thickness of the evaporated film is 20 nm; finally, a magnesium/silver alloy layer is sequentially evaporated on the electron transport layer to serve as a cathode layer of the device, wherein the evaporation rate of the magnesium/silver alloy layer is 2.0-3.0 nm/s, and the evaporation film thickness is 100 nm;
comparative device 1 was fabricated following the same procedure as above, except that the metal complex-doped material of the present invention was replaced with GD 01;
the materials used in this example have the following structure:
Figure BDA0002015270140000611
the device structures and data made using the metal complexes of the invention as doping materials following the same procedure as described above are summarized in the following table:
Figure BDA0002015270140000612
the test data for LE and EQE in the table is that the luminance of the element is 1000cd/m2Measured under the conditions of (1), the brightness and the lifetime data of the element were measured at a current density of 40mA/cm2Measured under the conditions of (1).
And (4) conclusion: according to the analysis of performance test results, the chromaticity coordinate of the metal complex phosphorescent material is in a green light region, the performance of the metal complex phosphorescent material far exceeds that of a known green light material, and the light-emitting service life of a device is very ideal.
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 (3)

1. Metal complex, characterized in that the molecular formula of the metal complex is Ir (LA2)2(LB77)、Ir(LA143)(LB82)2、Ir(LA912)(LB82)2Or Ir (LA471)3(ii) a The structures of LA2, LA143, LA471, LA912, LB77 and LB82 are as follows:
Figure FDA0003271784100000011
2. an organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers comprising the metal complex of claim 1 interposed between the first electrode and the second electrode, the organic layers being layers selected from the group consisting of an electron injection layer, an electron transport layer, a hole blocking layer, an electron blocking layer, a hole transport layer, a hole injection layer, an organic light emitting layer.
3. The organic electroluminescent device according to claim 2, wherein the organic layer is an organic light-emitting layer containing a host material and the metal complex of claim 1 doped in the host material,
the host material is selected from the group consisting of:
Figure FDA0003271784100000012
Figure FDA0003271784100000021
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080269491A1 (en) * 2007-02-13 2008-10-30 Arizona Board Of Regents For And On Behalf Of Arizona State University Organometallic Materials for Optical Emission, Optical Absorption, and Devices Including Organometallic Materials
CN103936791A (en) * 2013-12-12 2014-07-23 石家庄诚志永华显示材料有限公司 Series organic electrophosphorescent material
US20150060830A1 (en) * 2013-09-03 2015-03-05 University Of Southern California Organic electroluminescent materials and devices
US20170069855A1 (en) * 2014-02-28 2017-03-09 Arizona Board Of Regents On Behalf Of Arizona State University Chiral metal complexes as emitters for organic polarized electroluminescent devices
CN110128479A (en) * 2018-02-09 2019-08-16 环球展览公司 Electroluminescent organic material and device
CN111269267A (en) * 2018-12-05 2020-06-12 三星电子株式会社 Organometallic compound, and organic light emitting device and diagnostic composition including the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080269491A1 (en) * 2007-02-13 2008-10-30 Arizona Board Of Regents For And On Behalf Of Arizona State University Organometallic Materials for Optical Emission, Optical Absorption, and Devices Including Organometallic Materials
US20150060830A1 (en) * 2013-09-03 2015-03-05 University Of Southern California Organic electroluminescent materials and devices
CN103936791A (en) * 2013-12-12 2014-07-23 石家庄诚志永华显示材料有限公司 Series organic electrophosphorescent material
US20170069855A1 (en) * 2014-02-28 2017-03-09 Arizona Board Of Regents On Behalf Of Arizona State University Chiral metal complexes as emitters for organic polarized electroluminescent devices
CN110128479A (en) * 2018-02-09 2019-08-16 环球展览公司 Electroluminescent organic material and device
CN111269267A (en) * 2018-12-05 2020-06-12 三星电子株式会社 Organometallic compound, and organic light emitting device and diagnostic composition including the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis and characterization of phosphorescent platinum and iridium complexes with cyclometalated corannulene;John W. Facendola等;《Dalton Trans.》;20150210;第44卷;第8456-8466页 *

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