CN113292603A - Metal complex, organic electroluminescent device and application thereof - Google Patents

Metal complex, organic electroluminescent device and application thereof Download PDF

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CN113292603A
CN113292603A CN202110551601.1A CN202110551601A CN113292603A CN 113292603 A CN113292603 A CN 113292603A CN 202110551601 A CN202110551601 A CN 202110551601A CN 113292603 A CN113292603 A CN 113292603A
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ring
atoms
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metal complex
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曹建华
董智超
唐怡杰
邸庆童
郭文龙
赵雅妮
宋小东
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Beijing Bayi Space LCD Technology 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 Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0033—Iridium compounds
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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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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Abstract

The invention relates to a metal complex, an organic electroluminescent device and application thereof, wherein the metal complex is a pyrazine metal complex electrophosphorescent luminescent material with a condensed ring structure, and is obtained by taking modified pyrazine as a core and performing preparation processes such as ring closing and coordination.

Description

Metal complex, organic electroluminescent device and application thereof
Technical Field
The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a metal complex, an organic electroluminescent device and application thereof.
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.
Organic electroluminescent materials fall into two broad categories: organic electroluminescent materials and organic electrophosphorescent materials, in which organic electroluminescence is a result of radiative deactivation of singlet excitons, unlike photoluminescence, during which triplet excitons and singlet excitons are simultaneously generated. The generation ratio of singlet excitons and triplet excitons is generally 1: and 3, according to forbidden blocking effect of quantum statistics, triplet excitons mainly undergo non-radiative decay, have little contribution to luminescence, and only singlet excitons emit luminescence by radiation, so that the fundamental reason that the luminescence efficiency is difficult to improve for the organic/polymer electroluminescent device 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 assumption of triplet state luminescence, and the Forrest group made red electrophosphorescent light emitting devices by doping octaethylporphyrin platinum in a small molecular host material of octahydroxyquinoline aluminum, so that the external quantum efficiency reaches 4%, so far, the research of electrophosphorescence started to get great attention from academia, and the research of organic electrophosphorescence in the following years is rapidly developed. The iridium complex is a phosphorescent material which is developed most and has the best application prospect due to the short triplet state service life and the good luminescent performance, and the phosphorescent material has stronger triplet state quenching in a solid, so that generally the iridium complex is used as a doping object material, a material with a wider band gap is used as a doping host material, and high luminescent efficiency is obtained by energy transfer or direct exciton trapping on an object for luminescence.
Organic electroluminescent green phosphorescent materials are the earliest studied and the most mature materials. Hino et al in 2004 made phosphorescent devices by spin coating, the external quantum efficiency was at most 29cd/A, and the high efficiency achieved by this simple device structure was attributable to the good film-forming properties of the material and the energy transfer from host to guest material. Adachi et al doped (ppy)2Ir (acac) into TAZ and HMTPD as hole transport layer, obtained a green device with maximum external quantum efficiency of 20% and energy efficiency of 65lm/W, calculated that its internal quantum efficiency almost approached 100%, and triplet excitons and singlet excitons were simultaneously utilized.
At present, the red phosphorescent material still has the problems of low luminous quantum efficiency and poor color purity. The main reason for this is that red light comes from the transition between the narrower energy levels of the energy gap, while the heavy metal complex with narrow forbidden band has a certain difficulty in ligand design, and secondly, the system of red light 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 gap, which aggravates the quenching of phosphor and reduces the quantum yield of the red light system. Therefore, the design and synthesis of metal complexes with excellent comprehensive performance become an important subject of organic electroluminescent material research.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a metal complex, an organic electroluminescent device and application thereof.
In a first aspect of the present invention, there is provided a metal complex of the formulaComprises the following steps: m (L)A)x(LB)y(Lc)z，
Wherein M is a metal atom having an atomic weight greater than 40;
x represents an integer of 1,2 or 3; y represents an integer of 0, 1 or 2; z represents an integer of 0, 1 or 2; and x + y + z is equal to the oxidation state of metal M;
LAcomprises the following steps:
Figure BDA0003075688160000031
wherein R is1、R2、R3、R4、R5、R6And R7Each independently selected from one of a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, a cycloalkyl group, a heteroalkyl group, a heterocycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, an alkenyl group, a cycloalkenyl group, an isoalkenyl 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 thio group, a sulfonyl group, a sulfinyl group, a phosphino group, and a phosphino group; any adjacent substituents are optionally joined or fused to form a 5 or 6 membered ring or a polycyclic ring;
wherein ring B represents an aromatic or heteroaromatic ring containing at least two carbon atoms and is linked to ring a by a covalent bond;
wherein, X1Selected from carbon or nitrogen, and X1No substituent R being present for nitrogen3；
LBComprises the following steps:
Figure BDA0003075688160000032
wherein R is8、R9Each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, an alkane group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, a silane group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an aryl group, a heterocyclic aryl group, an aliphatic hydrocarbon group containing nitrogen, germanium, oxygen or sulfur, a phosphine group, and a phosphino group;
ring C and ring D are each independently selected from a five-membered carbocyclic ring, a five-membered heterocyclic ring, a six-membered carbocyclic ring or a six-membered heterocyclic ring; substituents R on ring C and ring D8、R9Is one or more than two, and R8、R9Wherein adjacent groups are optionally joined or fused to form a five-membered ring, a six-membered ring or a multiple ring;
wherein, X2、X3Selected from carbon or nitrogen, and X2And X3At least one is nitrogen;
LCcomprises the following steps:
Figure BDA0003075688160000041
wherein R is10、R11、R12Each independently selected from one of a hydrogen atom, a deuterium atom, a halogen atom, an alkane group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, a silane group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an aryl group, and a heterocyclic aryl group; and R is10、R11、R12Optionally joined or fused to form a five-membered, six-membered or polycyclic ring.
Further, the metal M is selected from Ir or Pt.
Further, the structural formula LAOne selected from the following structures:
Figure BDA0003075688160000042
Figure BDA0003075688160000051
further, the ring B is one of the following structures:
Figure BDA0003075688160000061
wherein V represents C (R)2NR, oxygen or sulfur; the dashed bonds represent the positions of connection to the metal M, "-" represents the positions of connection to the ring a, and furthermore:
w is, identically or differently at each occurrence, CR or N; or two adjacent groups W represent a group of the following formula (6) or (7),
Figure BDA0003075688160000062
wherein G represents C (R)2NR, oxygen or sulfur, Z represents, identically or differently at each occurrence, CR or N, and "^" represents the corresponding adjacent group W in formula (2), (3) or (5);
the radicals R, equal or different on each occurrence, being chosen from hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R13)2、C(＝O)Ar1、C(＝O)R13、P(＝O)(Ar1)2Having a structure of C1～C40Has a straight-chain alkyl group or has C1～C40Linear heteroalkyl group of (A) having C3～C40Is branched or cyclic alkyl or has C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Each of said radicals R may be substituted by one or more radicals R13Substitution of one or more non-adjacent-CH2The radicals may be substituted by R13C＝CR13、C≡C、Si(R13)2、Ge(R13)2、Sn(R13)2、C＝O、C＝S、C＝Se、C＝NR13、P(＝O)(R13)、SO、SO2、NR13O, S or CONR13And in which one or more hydrogen atoms can be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, aromatic or heteroaromatic cluster ring systems having from 5 to 80 aromatic ring atoms, preferably from 5 to 60 aromatic ring atoms, which can in each case be replaced by one or more radicals R13Substituted, having 5 toAn aryloxy or heteroaryloxy radical of 60 aromatic ring atoms which may be substituted by one or more radicals R13Substituted or a combination of these systems, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R13Substitution;
R13selected, identically or differently on each occurrence, from hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R14)2、C(＝O)Ar1、C(＝O)R14、P(＝O)(Ar1)2Having a structure of C1～C40Linear alkyl, alkoxy or thioalkyl of (2), having C1～C40Linear heteroalkyl group of (A) having C3～C40Branched or cyclic alkyl, alkoxy or thioalkyl of (2), having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl of (A), each R13The radicals being substituted by one or more radicals R14Substitution of one or more non-adjacent-CH2The radicals may be substituted by R14C＝CR14、C≡C、Si(R14)2、Ge(R14)2、Sn(R14)2、C＝O、C＝S、C＝Se、C＝NR14、P(＝O)(R14)、SO、SO2、NR14O, S or CONR14And in which one or more hydrogen atoms can be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which can in each case be replaced by one or more radicals R14Substituted aryloxy or heteroaryloxy radical having 5 to 60 atoms of the aromatic ring, which radical may be substituted by one or more radicals R14Substituted or a combination of these systems, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R14Substitution;
Ar1ar, which is the same or different at each occurrence1Is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which may be substituted by one or more nonaromatic radicals R14Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom1Can also be selected from N (R) through a single bond14)、C(R14)2Oxygen or sulfur bridging groups;
R14selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C1～C20Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R14They can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.
Further, said LAIs one of LA 1-LA 220, wherein the dotted line bond represents the position coordinated with the metal M, and the specific structures of LA 1-LA 220 are as follows:
Figure BDA0003075688160000071
Figure BDA0003075688160000081
Figure BDA0003075688160000091
Figure BDA0003075688160000101
Figure BDA0003075688160000111
Figure BDA0003075688160000121
Figure BDA0003075688160000131
further, said LBIs one of LB 1-LB 220, and the specific structures of LB 1-LB 220 are as follows:
Figure BDA0003075688160000132
Figure BDA0003075688160000141
Figure BDA0003075688160000151
Figure BDA0003075688160000161
Figure BDA0003075688160000171
Figure BDA0003075688160000181
Figure BDA0003075688160000191
Figure BDA0003075688160000201
further, Lc is one of Lc 1-Lc 40, and the specific structures of Lc 1-Lc 40 are as follows:
Figure BDA0003075688160000202
Figure BDA0003075688160000211
further, the metal complex has a formula of Ir (LAi) (LBj) (LCw), Ir (LAi)2(LBj)、Ir(LAi)3、Ir(LAi)2(LCw), Pt (LAi) (LBj) or Pt (LAi) (LCw);
wherein i is an integer of 1 to 220, j is an integer of 1 to 220, and w is an integer of 1 to 40;
furthermore, the molecular formula of the metal complex is Ir (LA) (LB) (LC), Ir (LA)2(LB)、Ir(LA)3、Ir(LA)2(LC), Pt (LA) (LB), or Pt (LA) (LC).
A second object of the present invention is to provide an organic electroluminescent device, which includes a substrate, an anode layer disposed on the substrate, a hole transport layer disposed on the anode layer, an organic light emitting layer disposed on the hole transport layer, an electron transport layer disposed on the organic light emitting layer, and a cathode layer disposed on the electron transport layer; the material of the organic light-emitting layer comprises one or more of the metal complexes M (LA) x (LB) y (lc) z.
The material for an organic light-emitting element may be formed using the organometallic complex of the present invention alone, or may contain other compounds.
The organometallic complex of the present invention contained in the material for an organic electroluminescent element of the present invention can be used as a host material, a dopant material, or a carrier transporting material. In this case, the material for an organic electroluminescent element of the present invention may contain other compounds as auxiliary materials.
The organic electroluminescent element includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injecting layers, hole-transporting layers, hole-blocking layers, electron-transporting layers, electron-injecting layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, exciton blocking function can likewise be introduced between the two light-emitting layers. However, it should be noted that each of these layers need not be present. The organic electroluminescent element described herein may include one light-emitting layer, or it may include a plurality of light-emitting layers. I.e. a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred are systems with three light-emitting layers, wherein the three layers can exhibit blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises, according to the invention, a compound according to the invention.
The organic electroluminescent element according to the invention does not comprise a separate hole-injecting layer and/or hole-transporting layer and/or hole-blocking layer and/or electron-transporting layer, i.e. the light-emitting layer is directly adjacent to the hole-injecting layer or the anode and/or the light-emitting layer is directly adjacent to the electron-transporting layer or the electron-injecting layer or the cathode, as described in, for example, WO 2005053051.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole-injecting and hole-transporting layer and in the electron-injecting and electron-transporting layer, all materials can be used in the manner conventionally used according to the prior art. The person skilled in the art will thus be able to use all materials known for organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Preference is furthermore given to organic electroluminescent elements in which one or more layers are applied by means of a sublimation process in which the temperature in a vacuum sublimation apparatus is below 10-5Mbar, preferably below 10-6The material is applied by vapour deposition at an initial pressure of mbar. However, the initial pressure may also be even lower, e.g. below 10-7Millibar.
Further, preferred are organic electroluminescent elements by means of organic vapour deposition methods or by means of organic vapour deposition methodsSublimation of carrier gas to apply one or more layers, wherein at 10-5The material is applied at a pressure between mbar and 1 bar. A particular example of this method is the organic vapour jet printing method, in which the material is applied directly through a nozzle and is therefore structured.
Preference is furthermore given to organic electroluminescent elements which are characterized in that one or more layers are produced from solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, ink-jet printing or nozzle printing. Soluble compounds, for example obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, hybrid methods are possible, in which, for example, one or more layers are applied from solution and one or more further layers are applied by vapor deposition.
These methods are generally known to those skilled in the art, and they can be applied to an organic electroluminescent element comprising the compound according to the present invention without inventive labor.
The invention therefore also relates to a method for producing the organic electroluminescent element according to the invention, at least one layer being applied by means of a sublimation method and/or at least one layer being applied by means of an organic vapour deposition method or by means of carrier gas sublimation and/or at least one layer being applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to compositions comprising at least one organometallic compound as indicated above. The same preferences as indicated above for the organic electroluminescent elements apply to the compounds according to the invention. In particular, the compounds may furthermore preferably comprise further compounds. The processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires the preparation of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferred to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchytone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylanisole, 3, 5-dimethylanisole, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1, 1-bis (3, 4-dimethylphenyl) ethane, or a mixture of these solvents.
Further, an organic light emitting layer in the organic electroluminescent device is doped in the host material to emit light or emit non-doped light;
the host material is selected from one or more of the following compounds:
Figure BDA0003075688160000241
the third object of the invention provides an application of the metal complex in preparing an organic electroluminescent device or an organic electroluminescent material.
Compared with the prior art, the invention has the beneficial effects that:
the metal complex is a pyrazine metal complex electrophosphorescent luminescent material with a condensed ring structure, is obtained by taking modified pyrazine as a core and through preparation processes such as ring closing, coordination and the like, is deep red in electroluminescence, high in luminous efficiency, good in thermal stability, easy to prepare, easy to sublimate and purify and has a very wide market prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic view of bottom emission of an organic electroluminescent device of the present invention;
FIG. 2 is a schematic view of a top emission of the organic electroluminescent device of the present invention;
FIG. 3 is a graph showing electroluminescence spectra of organic electroluminescence devices EL-1, EL-3, EL-4 and EL-6 in the present invention.
Reference numerals
1-substrate, 2-anode layer, 3-hole injection layer, 4-hole transmission/electron blocking layer, 5-organic light emitting layer, 6-hole blocking/electron transmission layer, 7-electron injection layer and 8-cathode layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
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 series of novel metal complexes provided by the present invention, all reactions being carried out under well-known suitable conditions, some involving simple organic preparations, for example the preparation of phenylboronic acid derivatives, can be synthesized by skilled operative skills and are not described in detail herein.
The following abbreviations are used in the examples of the present invention and are specifically shown in table 1:
TABLE 1
Abbreviations Full scale
THF Tetrahydrofuran (THF)
n-BuLi N-butyl lithium
DMF N, N-dimethylformamide
Pd(PPh3)4 Tetrakis (triphenylphosphine) palladium
[IrCl(COD)]2 (1, 5-cyclooctadiene) iridium chloride dimer
Pd2(dba)3CHCl3 Tris (dibenzylideneacetone) dipalladium-chloroform adduct
Example 1
Preparation of compound LA 27:
the preparation method of the ligand LA27 specifically comprises the following steps:
the first step is as follows: preparation of Compound Int-1
Figure BDA0003075688160000261
11.0mmol of o-iodonitrobenzene, 10.0mmol of 3, 4-diethylpyrrole, 1.2g (12.0mmol) of sodium tert-butoxide and a further 52mg (0.05mmol) of Pd2(dba)3CHCl3The catalyst, 0.05mL of 10% tri-tert-butylphosphine toluene solution and 60mL of toluene are heated to 90 ℃ under the protection of nitrogen, stirred and reacted for 12 hours, cooled to room temperature, diluted by adding 60mL of water, extracted by ethyl acetate, dried by organic phase, filtered, concentrated and dried by reduced pressure, and separated and purified by a silica gel column to obtain the compound Int-1, yellow solid with the yield of 92%.
The second step is that: preparation of Compound Int-2
Figure BDA0003075688160000262
10.0mmol of the intermediate Int-1 prepared in the first step, 50.0mmol of iron powder, 50.0mmol of ammonium chloride and 150mL of ethanol are mixed, 10mL of water is added, the mixture is stirred and reacted for 5 hours at room temperature, the filtrate is concentrated and dried, and the filtrate is separated and purified by a silica gel column to obtain the intermediate Int-2 which is yellow solid with the yield of more than 90%.
The third step: preparation of compound LA27
Figure BDA0003075688160000271
15.0mmol of the intermediate Int-2 prepared in the second step is dissolved in 50mL of dimethyl sulfoxide, under the protection of nitrogen, 22.5mmol of ethyl 3, 5-dimethylbenzoyl acetate and 7.5mmol of p-toluenesulfonic acid hydrate are added, the temperature is raised to 120 ℃, the reaction is stirred for 12 hours, the mixture is cooled to room temperature, 200mL of saturated aqueous ammonium chloride solution is added, the mixture is filtered, a filter cake is washed by water and ethanol, and the mixture is separated and purified by a silica gel column to obtain a compound LA27 which is yellow solid and has the yield of 85%.
HRMS：329.2043[M+H]；1H-NMR(CDCl3,TMS)δ1.25(s,3H),1.72(s,3H),2.40(s,6H),3.04～3.09(m,4H),7.09(s,1H),7.42(s,1H),7.55～7.63(m,2H),7.79～7.86(m,3H),8.39～8.41(d,1H)。
Example 2
Referring to the preparation method of example 1, compounds LA1 to LA26, LA28 to LA70, and LA91 to LA120 were prepared by substituting o-iodonitrobenzene having different substituents for o-iodonitrobenzene in the first step in example 1, substituting pyrrole having different substituents for 3, 4-diethylpyrrole in the first step in example 1, substituting ethyl formylacetate having different substituents for ethyl 3, 5-dimethylbenzoylacetate in the third step in example 1, and adaptively adjusting other experimental parameters to prepare LA1 to LA26, LA28 to LA70, and LA91 to LA120 in ligand LA.
Example 3
Preparation of compound LA 85:
the preparation method of the ligand LA85 comprises the following steps:
the first step is as follows: preparation of Compound Int-3
Figure BDA0003075688160000281
20.0mmol of phthalic diamide, 24.0mmol of phenylacetaldehyde and 2.0g (60.0mmol) of sublimed sulfur, 150mL of DMF are added, the temperature is raised to 100 ℃ under stirring, the mixture is stirred and reacted for 12 hours, the mixture is cooled to room temperature, 300mL of water is added for dilution, the mixture is extracted by ethyl acetate, organic phase is dried, filtered, filtrate is concentrated and dried under reduced pressure, and the mixture is separated and purified by a silica gel column, so that a compound Int-3 is obtained, yellow solid is obtained, and the yield is 85%.
The second step is that: preparation of Compound Int-4
Figure BDA0003075688160000282
11.0mmol of o-iodonitrobenzene and 10.0mmol of the intermediate Int-3 prepared in the first step, 2.8g (20.0mmol) of anhydrous potassium carbonate, 95.0mg (0.5mmol) of a ketone iodide catalyst, 0.05mL of 1, 2-dimethylethylenediamine and 80mL of toluene are added, the mixture is heated to 110 ℃ under the protection of nitrogen and stirred for reaction for 12 hours, the mixture is cooled to room temperature, filtered, the filtrate is concentrated and dried under reduced pressure, and is separated and purified by a silica gel column, so that the compound Int-4 is obtained, and yellow solid is obtained with the yield of 90%.
The third step: preparation of compound LA85
Figure BDA0003075688160000283
10.0mmol of the intermediate Int-4 prepared in the second step, 50.0mmol of iron powder and 150mL of glacial acetic acid are mixed, stirred, heated and refluxed for 5 hours, cooled to room temperature, filtered, concentrated and dried in filtrate, and separated and purified by a silica gel column to obtain the compound LA85 as a yellow solid with the yield of 86%.
HRMS：296.1212[M+H]；1H-NMR(CDCl3,TMS)δ7.26～7.38(m,2H),7.42～7.45(m,1H),7.55～7.59(m,2H),7.75～7.92(m,5H),8.38～8.40(d,2H),8.44(s,1H)。
Example 4
Preparation of compounds LA 71-LA 84 and LA 86-LA 90 referring to the preparation method of example 3, phenylacetaldehyde with different substituents was substituted for phenylacetaldehyde in the first step of example 3, and other experimental parameters were adaptively adjusted to prepare LA 71-LA 84 and LA 86-LA 90 in ligand LA.
Example 5
Preparation of compound LA 154:
the preparation method of the ligand LA154 comprises the following steps:
the first step is as follows: preparation of Compound Int-5
Figure BDA0003075688160000291
20.0mmol of 2- (tert-butyl formate) aminobenzaldehyde, 60.0mmol of anhydrous potassium carbonate and 24.0mmol of bromoacetylbenzene, 100mL of dried acetonitrile is added, the mixture is stirred and reacted for 12 hours at room temperature, the filtrate is filtered, concentrated and dried under reduced pressure, 100mL of water is added for dilution, the mixture is extracted by ethyl acetate, the organic phase is dried, the filtrate is concentrated and dried under reduced pressure, 100mL of acetonitrile and 5mL of concentrated hydrochloric acid are added into the residue, the mixture is stirred and heated for reflux reaction for 2 hours, the mixture is cooled to room temperature, 5.0g of anhydrous potassium carbonate is added, the mixture is stirred and reacted for 1 hour, the filtrate is filtered, concentrated and dried under reduced pressure, and the mixture is separated and purified by a silica gel column, so that the compound Int-5 is obtained as a yellow solid, and the yield is 77%.
The second step is that: preparation of Compound Int-6
Figure BDA0003075688160000292
10.0mmol of the intermediate Int-5 prepared in the first step was dissolved in 100mL of dry THF, cooled to 0 ℃ in an ice salt bath, 11.0mmol of sodium hydride solid was added in portions, stirred for 1 hour, 11.0mmol of bromoacetal was added, warmed to room temperature, stirred for 12 hours, 5mL of ice water was added dropwise, the organic phase was separated, extracted with ethyl acetate, dried, filtered, concentrated under reduced pressure and dried, and separated and purified by a silica gel column to obtain the compound Int-6 as a yellow oil with a yield of 92%.
The third step: preparation of Compound Int-7
Figure BDA0003075688160000301
10.0mmol of the intermediate Int-6 prepared in the second step is dissolved in 80mL of glacial acetic acid, 11.0mmol of ammonium acetate and 1.0mmol of p-toluenesulfonic acid are added, the mixture is heated up, refluxed, stirred and reacted for 12 hours, cooled to room temperature, concentrated and dried under reduced pressure, and separated and purified by a silica gel column to obtain the compound Int-7, a yellow solid, and the yield is 72%.
The fourth step: preparation of compound LA154
Figure BDA0003075688160000302
10.0mmol of the intermediate Int-7 prepared in the third step is dissolved in 100mL of dry THF, under the protection of nitrogen, 11.0mmol of potassium tert-butoxide is added, the temperature is reduced to-78 ℃ by liquid nitrogen, 11.0mmol of n-butyllithium-hexane solution is added dropwise, the mixture is stirred and reacted for 30 minutes, 11.0mmol of 2-bromopropane is added dropwise, the mixture is stirred and reacted for 1 hour, the temperature is raised to room temperature and the reaction is carried out for 1 hour, 10mL of saturated aqueous ammonium chloride solution is added dropwise, an organic phase is separated, the organic phase is extracted by ethyl acetate, the organic phase is dried, filtered, the filtrate is concentrated and dried under reduced pressure, and is separated and purified by a silica gel column, so that the compound LA154 is obtained, a yellow solid, and the yield is 84%.
HRMS：315.1887[M+H]；1H-NMR(CDCl3,TMS)δ1.46(s,6H),2.40(s,6H),3.95～3.98(m,1H),6.95(s,1H),7.15～7.19(m,2H),7.68～7.71(d,1H),7.75(s,2H),8.12～8.14(d,1H),8.16～8.17(d,1H),8.32～8.33(d,1H)。
Example 6
Preparation of compounds LA 121-LA 153 and LA 155-LA 175 with reference to the preparation method of example 5, bromoacetylbenzene with different substituents is used to replace bromoacetylbenzene in the first step of example 5, different alkyl halides are used to replace 2-bromopropane in the fourth step of example 5, and other experimental parameters are adaptively adjusted to prepare LA 121-LA 153 and LA 155-LA 175 in ligand LA.
Example 7
Preparation of compound LA 194:
the preparation method of ligand LA194 comprises the following steps:
the first step is as follows: preparation of Compound Int-8
Figure BDA0003075688160000311
20.0mmol of indole-2-carboxylic acid ethyl ester, 40.0mmol of anhydrous cesium carbonate and 24.0mmol of bromoacetylbenzene, then 100mL of dried acetonitrile and 2.5mmol of potassium iodide are added, the temperature is raised to 70 ℃, the mixture is stirred and reacted for 24 hours, the mixture is cooled to room temperature, the filtrate is filtered, the filtrate is concentrated and dried under reduced pressure, and the product is separated and purified by a silica gel column to obtain the compound Int-8, a yellow solid with the yield of 58%.
The second step is that: preparation of Compound Int-9
Figure BDA0003075688160000312
10.0mmol of the intermediate Int-8 prepared in the first step is dissolved in 80mL of n-butanol and 20mL of acetic acid, 12.0mmol of ammonium acetate is added, the temperature is raised to 150 ℃ by using an oil bath, stirring is carried out for reaction for 12 hours, the temperature is cooled to room temperature, 500mL of ice water is added, stirring and filtering are carried out, a filter cake is washed by water and recrystallized by ethanol, and the compound Int-9 is obtained as a white solid with the yield of 75%.
The third step: preparation of Compound Int-10
Figure BDA0003075688160000321
Dissolving 10.0mmol of the intermediate Int-9 prepared in the second step in 50mL of phosphorus oxychloride, adding 1.0mmol of phosphorus pentachloride, heating, refluxing, stirring, reacting for 12 hours, cooling to room temperature, concentrating and drying under reduced pressure, adding crushed ice to quench the reaction, stirring, extracting with ethyl acetate, collecting an organic phase, drying, filtering, concentrating and drying the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain a compound Int-10, namely a yellow solid, wherein the yield is 84%.
The fourth step: preparation of compound LA194
Figure BDA0003075688160000322
10.0mmol of the intermediate Int-10 prepared in the third step is dissolved in 80mL of THF, 20.0mmol of isobutylboronic acid and 40.0mmol of anhydrous sodium bicarbonate are added under the protection of nitrogen, 0.1mmol of palladium acetate and 10mL of water are added, the mixture is heated to reflux for 12 hours, 20mL of saturated saline solution is added, an organic phase is separated, an aqueous phase is extracted by ethyl acetate, the organic phase is dried, filtered, and the filtrate is concentrated and dried under reduced pressure and is separated and purified by a silica gel column, so that the compound LA194 is obtained as yellow oily matter with the yield of 82%.
HRMS：329.2041[M+H]；1H-NMR(CDCl3,TMS)δ0.86(s,6H),1.82～1.85(m,1H),2.41(s,6H),2.90(s,2H),6.94(d,2H),7.06～7.14(m,2H),7.68～7.70(m,3H),8.23(s,1H),8.52(s,1H)。
Example 8
Preparation of compounds LA176 to LA193 and LA195 to LA220 referring to the preparation method of example 7, bromoacetylbenzene with different substituents is substituted for bromoacetylbenzene in the first step of example 7, different boronic acids are substituted for isobutylboronic acid in the fourth step of example 7, and other experimental parameters are adaptively adjusted to prepare LA176 to LA193 and LA195 to LA220 in ligand LA.
Example 9
Compound Ir (LA14)2Preparation of (LC 4):
metal complex Ir (LA14)2(LC4) a method for preparing comprising the steps of:
the first step is as follows: preparation of Compound Int-11
Figure BDA0003075688160000331
2.7g of the compound LA14 and 1.4g of IrCl3·3H2O is dispersed in 48ml of ethylene glycol ethyl ether and 16ml of water, the temperature is increased under the protection of nitrogen, reflux reaction is carried out for 24 hours, the mixture is cooled to room temperature, filtration is carried out, a filter cake is washed by water and vacuum drying is carried out, and 2.8g of compound Int-11, brown solid, is obtained.
The second step is that: compound Ir (LA14)2Preparation of (LC4)
Figure BDA0003075688160000332
2.0g of the compound Int-11 and 620mg of 3, 7-diethylnonane-4, 6-dione and 1.24g of anhydrous sodium carbonate are dispersed in 40ml of acetonitrile and 40ml of chloroform, the reaction is refluxed at elevated temperature for 24 hours under nitrogen protection, cooled to room temperature and the reaction is quenchedPouring the reaction solution into water, extracting with dichloromethane, drying the organic phase, filtering, concentrating the filtrate under reduced pressure, and purifying the residue with silica gel column to obtain 1.3g of compound Ir (LA14)2(LC4), a reddish brown solid.
Example 10
Compound Ir (LA154)2Preparation of (LC 9):
metal complex Ir (LA154)2(LC9) a method for preparing comprising the steps of:
the first step is as follows: preparation of Compound Int-12
Figure BDA0003075688160000341
2.0g of the compound LA154 and 1.0g of IrCl3·3H2O is dispersed in 48ml of ethylene glycol ethyl ether and 16ml of water, the temperature is increased under the protection of nitrogen, reflux reaction is carried out for 24 hours, the mixture is cooled to room temperature, filtration is carried out, a filter cake is washed by water and vacuum drying is carried out, and 2.1g of compound Int-12, brown solid, is obtained.
The second step is that: compound Ir (LA154)2Preparation of (LC9)
Figure BDA0003075688160000342
2.0g of compound Int-12 and 730mg of 1, 3-dicyclopentylpropane-1, 3-dione and 1.24g of anhydrous sodium carbonate are dispersed in 40ml of acetonitrile and 40ml of chloroform, the mixture is heated under reflux for 24 hours under nitrogen protection, the mixture is cooled to room temperature, the reaction solution is poured into water, extraction is carried out with dichloromethane, the organic phase is dried, filtration is carried out, the filtrate is concentrated under reduced pressure and dried, and the residue is separated and purified by a silica gel column to obtain 1.4g of compound Ir (LA154)2(LC9), brown solid.
Example 11
With reference to the preparation methods of example 9 and example 10, the compounds of the present invention were prepared: ir (LAi)2(LCw), i is an integer of 1 to 220, and w is an integer of 1 to 40.
Example 12
Preparation of compound Ir (LA22) (LB170) (LC 7):
the preparation method of the metal complex Ir (LA22) (LB170) (LC7) comprises the following steps:
the first step is as follows: preparation of Compound Int-13
Figure BDA0003075688160000351
340.8mg of 1-phenyl-1H-imidazolium iodomethane salt and 139.5mg of silver oxide were dispersed in 20mL of methylene chloride, 400mg of 4A molecular sieve was added thereto, the mixture was stirred at room temperature for reaction for 2 hours, and 1.4g of [ IrCl (COD)]2The reaction was stirred for 2 hours, filtered, the filter cake was washed with dichloromethane, concentrated and dried under reduced pressure, 50mL of n-hexane was added, filtered and dried under vacuum to give 0.5g of compound Int-13 as a yellow solid.
The second step is that: preparation of Compound Ir (LA22) (LB170) (LC7)
Figure BDA0003075688160000352
0.5g of the compound Int-13 prepared in the above step was mixed with 332.0mg (1.01mmol) of LA22 and 50mL of methanol, and the mixture was heated under reflux for 5 days under nitrogen protection, cooled to room temperature, filtered, and the filter cake was washed with methanol to give a brown solid.
The resulting brown solid was dispersed with 157.5mg of 2, 6-dimethylheptane-3, 5-dione and 97mg of sodium tert-butoxide in 40ml of anhydrous THF, refluxed at elevated temperature under nitrogen for 1 hour, cooled to room temperature, concentrated and dried under reduced pressure, and the residue was separated and purified by a silica gel column to give 220mg of compound Ir (LA22) (LB170) (LC7) as a reddish brown solid.
Example 13
Referring to example 12, compounds of the invention were prepared: ir (LAi) (LBj) (LCw); wherein i is an integer of 1 to 220, j is an integer of 1 to 220, and w is an integer of 1 to 40.
Example 14
Compound Ir (LA194)3The preparation of (1):
Figure BDA0003075688160000361
0.5g of Ir prepared as in example 11 (LA194)2(LC1) was mixed with 347mg of LA194, and the mixture was dispersed with 20mL of glycerin under stirring, heated to 180 ℃ under nitrogen atmosphere, stirred to react for 8 hours, cooled to room temperature, poured into 200mL of 1N diluted hydrochloric acid, filtered, the cake was washed with water, ethanol and ether, and the resulting solid was separated and purified by silica gel column to obtain 0.27g of Ir (LA194)3A reddish brown solid.
Example 15
Referring to example 14, compounds of the invention were prepared: ir (LAi)3(ii) a Wherein i is an integer of 1 to 220.
Example 16
Preparation of compound Pt (LA7) (LC 2):
a preparation method of a metal complex Pt (LA7) (LC2) comprises the following steps:
the first step is as follows: preparation of Compound Int-14
Figure BDA0003075688160000362
Into a 100mL reaction flask, 0.5g of LA7, 12mL of ethylene glycol ethyl ether and 4mL of water were charged, 0.7g of potassium tetrachloroplatinate was added, the mixture was heated under reflux for 12 hours, cooled to room temperature, filtered, and the filter cake was washed with water and ethanol, and vacuum-dried to obtain 0.65g of compound Int-14 as a brown solid.
The second step is that: synthesis of Compound Pt (LA7) (LC2)
Figure BDA0003075688160000371
Into a 100mL reaction flask, 0.5g of the intermediate Int-14 prepared in the above step, 20mL of acetonitrile and 20mL of chloroform were charged, 0.3g of sodium carbonate and 190mg of 2,2,6, 6-tetramethylheptane-3, 5-dione were added, the mixture was refluxed at elevated temperature for 12 hours, cooled to room temperature, poured into 200mL of water, extracted with chloroform, dried with organic phase, concentrated under reduced pressure and dried, and separated and purified by silica gel column to obtain 0.44g of a product of formula Pt (LA7) (LC2) as a red solid.
Example 17
Referring to example 16, compounds of the invention were prepared: pt (LAi) (LCw); wherein i is an integer of 1 to 220, and w is an integer of 1 to 40.
Fig. 1 and 2 are schematic views of bottom emission and bottom emission examples of an organic electroluminescent device according to the present invention, respectively.
Example 18
An OLED device according to this embodiment, as shown in fig. 1, includes 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 8 disposed on the electron transport layer 6.
The preparation method of the OLED device comprises the following steps:
(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 and respectively evaporating a compound DNTPD on the anode layer film to be used as a hole injection layer, 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) and continuously evaporating a layer of the compound and TDC of the invention on the hole transport layer to be used as a light emitting layer of the device, wherein the TDC is a main material and the metal complex of the invention is a doping material, and the evaporation rate ratio of the doping material to the TDC is 1: 100, the doping concentration of the metal complex is 1-10%, the total evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 50 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 example 1
A comparative device EL-1 was fabricated in the same manner as in example 18, except that the metal complex doped material of the present invention was replaced with RD-1.
The specific structures of the materials used in example 18 and comparative example 1 are shown below:
Figure BDA0003075688160000381
test examples
Devices EL-2 to EL-7 were fabricated by the method of example 18 using the different metal complexes prepared in accordance with the present invention as doping materials, and the test results are shown in Table 2.
Among them, the electroluminescence spectra of the organic electroluminescence devices EL-1, EL-3, EL-4 and EL-6 are shown in FIG. 3.
TABLE 2
Figure BDA0003075688160000391
From the analysis of the results of the performance tests, the metal complex of the present invention had a chromaticity coordinate in the deep red region and an initial luminance of 2000cd/cm2Under these conditions, the luminance decay of the test device is much better than that of the contrast device.
The inventors also conducted the above experiments on the metal complexes prepared in other examples, and the results were substantially consistent and, due to the limited space, are not listed.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. A metal complex of the formula: m (L)A)x(LB)y(Lc)z，
Wherein M is a metal atom having an atomic weight greater than 40;
x represents an integer of 1,2 or 3; y represents an integer of 0, 1 or 2; z represents an integer of 0, 1 or 2; and x + y + z is equal to the oxidation state of metal M;
LAcomprises the following steps:
Figure FDA0003075688150000011
wherein R is1、R2、R3、R4、R5、R6And R7Each independently selected from one of a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, a cycloalkyl group, a heteroalkyl group, a heterocycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, an alkenyl group, a cycloalkenyl group, an isoalkenyl 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 thio group, a sulfonyl group, a sulfinyl group, a phosphino group, and a phosphino group; any adjacent substituents are optionally joined or fused to form a 5 or 6 membered ring or a polycyclic ring;
wherein ring B represents an aromatic or heteroaromatic ring containing at least two carbon atoms and is linked to ring a by a covalent bond;
wherein, X1Selected from carbon or nitrogen, and X1No substituent R being present for nitrogen3；
LBComprises the following steps:
Figure FDA0003075688150000021
wherein R is8、R9Each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, an alkane group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, a silane group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an aryl group, a heterocyclic aryl group, an aliphatic hydrocarbon group containing nitrogen, germanium, oxygen or sulfur, a phosphine group, and a phosphino group;
ring C and ring D are each independently selected from a five-membered carbocyclic ring, a five-membered heterocyclic ring, a six-membered carbocyclic ring or a six-membered heterocyclic ring; substituents R on ring C and ring D8、R9Is one or more than two, and R8、R9Wherein adjacent groups are optionally joined or fused to form a five-membered ring, a six-membered ring or a multiple ring;
wherein, X2、X3Selected from carbon or nitrogen, and X2And X3At least one is nitrogen;
LCcomprises the following steps:
Figure FDA0003075688150000022
wherein R is10、R11、R12Each independently selected from one of a hydrogen atom, a deuterium atom, a halogen atom, an alkane group, a cycloalkyl group, a heteroalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, a silane group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an aryl group, and a heterocyclic aryl group; and R is10、R11、R12Optionally joined or fused to form a five-membered, six-membered or polycyclic ring.
2. The metal complex according to claim 1, wherein the metal M is selected from Ir or Pt.
3. The metal complex of claim 1, wherein the formula LAOne selected from the following structures:
Figure FDA0003075688150000031
Figure FDA0003075688150000041
4. the metal complex of claim 1, wherein ring B is one of the following structures:
Figure FDA0003075688150000042
wherein V represents C (R)2NR, oxygen or sulfur; the dashed bonds represent the positions of connection to the metal M, "-" represents the positions of connection to the ring a, and furthermore:
w is, identically or differently at each occurrence, CR or N; or two adjacent groups W represent a group of the following formula (6) or (7),
Figure FDA0003075688150000043
wherein G represents C (R)2NR, oxygen or sulfur, Z represents, identically or differently at each occurrence, CR or N, and "^" represents the corresponding adjacent group W in formula (2), (3) or (5);
the radicals R, equal or different on each occurrence, being chosen from hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R13)2、C(＝O)Ar1、C(＝O)R13、P(＝O)(Ar1)2Having a structure of C1～C40Has a straight-chain alkyl group or has C1～C40Linear heteroalkyl group of (A) having C3～C40Is branched or cyclic alkyl or has C3～C40A branched or cyclic heteroalkyl group of,Having a structure of C2～C40Each of said radicals R may be substituted by one or more radicals R13Substitution of one or more non-adjacent-CH2The radicals may be substituted by R13C＝CR13、C≡C、Si(R13)2、Ge(R13)2、Sn(R13)2、C＝O、C＝S、C＝Se、C＝NR13、P(＝O)(R13)、SO、SO2、NR13O, S or CONR13And in which one or more hydrogen atoms can be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, aromatic or heteroaromatic cluster ring systems having from 5 to 80 aromatic ring atoms, preferably from 5 to 60 aromatic ring atoms, which can in each case be replaced by one or more radicals R13Substituted aryloxy or heteroaryloxy radical having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R13Substituted or a combination of these systems, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R13Substitution;
R13selected, identically or differently on each occurrence, from hydrogen atoms, deuterium atoms, halogen atoms, nitrile groups, nitro groups, N (Ar)1)2、N(R14)2、C(＝O)Ar1、C(＝O)R14、P(＝O)(Ar1)2Having a structure of C1～C40Linear alkyl, alkoxy or thioalkyl of (2), having C1～C40Linear heteroalkyl group of (A) having C3～C40Branched or cyclic alkyl, alkoxy or thioalkyl of (2), having C3～C40A branched or cyclic heteroalkyl group of (A) having C2～C40Alkenyl or alkynyl of (A), each R13The radicals being substituted by one or more radicals R14Substitution of one or more non-adjacent-CH2The radicals may be substituted by R14C＝CR14、C≡C、Si(R14)2、Ge(R14)2、Sn(R14)2、C＝O、C＝S、C＝Se、C＝NR14、P(＝O)(R14)、SO、SO2、NR14O, S or CONR14And in which one or more hydrogen atoms can be replaced by deuterium atoms, halogen atoms, nitrile groups or nitro groups, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which can in each case be replaced by one or more radicals R14Substituted aryloxy or heteroaryloxy radical having 5 to 60 atoms of the aromatic ring, which radical may be substituted by one or more radicals R14Substituted or a combination of these systems, wherein two or more adjacent substituents R may optionally be joined or fused to form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R14Substitution;
Ar1ar, which is the same or different at each occurrence1Is an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms which may be substituted by one or more nonaromatic radicals R14Substitution; two groups Ar here bonded to the same nitrogen or phosphorus atom1Can also be selected from N (R) through a single bond14)、C(R14)2Oxygen or sulfur bridging groups;
R14selected from hydrogen atom, deuterium atom, fluorine atom, nitrile group, having C1～C20Wherein one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups, wherein two or more adjacent substituents R14They can form mono-or polycyclic aliphatic, aromatic or heteroaromatic ring systems with one another.
5. The metal complex of any one of claims 1 to 4, wherein L isAIs one of LA 1-LA 220, wherein the dotted line bond represents the position coordinated with the metal M, and the specific structures of LA 1-LA 220 are as follows:
Figure FDA0003075688150000061
Figure FDA0003075688150000071
Figure FDA0003075688150000081
Figure FDA0003075688150000091
Figure FDA0003075688150000101
Figure FDA0003075688150000111
6. the metal complex of any one of claims 1 to 4, wherein L isBIs one of LB 1-LB 220, and the specific structures of LB 1-LB 220 are as follows:
Figure FDA0003075688150000112
Figure FDA0003075688150000121
Figure FDA0003075688150000131
Figure FDA0003075688150000141
Figure FDA0003075688150000151
Figure FDA0003075688150000161
Figure FDA0003075688150000171
Figure FDA0003075688150000181
7. the metal complex as claimed in any one of claims 1 to 4, wherein Lc is one of LC 1-LC 40, and LC 1-LC 40 have the following specific structures:
Figure FDA0003075688150000182
Figure FDA0003075688150000191
8. the metal complex of any one of claims 1-7, wherein the metal complex has the formula Ir (LAi) (LBj) (LCw), Ir (LAi)2(LBj)、Ir(LAi)3、Ir(LAi)2(LCw), Pt (LAi) (LBj) or Pt (LAi) (LCw);
wherein i is an integer of 1 to 220, j is an integer of 1 to 220, and w is an integer of 1 to 40;
preferably, the molecular formula of the metal complex is Ir (LA), (LB) (LC), Ir (LA)2(LB)、Ir(LA)3、Ir(LA)2(LC), Pt (LA) (LB), or Pt (LA) (LC).
9. An organic electroluminescent device comprises a substrate, an anode layer arranged on the substrate, a hole transport layer arranged on the anode layer, an organic light emitting layer arranged on the hole transport layer, an electron transport layer arranged on the organic light emitting layer, and a cathode layer arranged on the electron transport layer; characterized in that the material of the organic light-emitting layer comprises one or more of the metal complexes M (LA) x (LB) y (lc) z according to any one of claims 1 to 8;
preferably, the organic light-emitting layer in the organic electroluminescent device is doped in the host material to emit light or emit non-doped light;
the host material is selected from one or more of the following compounds:
Figure FDA0003075688150000201
10. use of a metal complex according to any one of claims 1 to 8 for the preparation of an organic electroluminescent device or for the preparation of an organic electroluminescent material.
CN202110551601.1A 2021-05-20 2021-05-20 Metal complex, organic electroluminescent device and application thereof Pending CN113292603A (en)

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