CN114437138A - Metal complex and organic electroluminescent device - Google Patents

Metal complex and organic electroluminescent device Download PDF

Info

Publication number
CN114437138A
CN114437138A CN202210072706.3A CN202210072706A CN114437138A CN 114437138 A CN114437138 A CN 114437138A CN 202210072706 A CN202210072706 A CN 202210072706A CN 114437138 A CN114437138 A CN 114437138A
Authority
CN
China
Prior art keywords
group
ring
metal complex
membered
lai
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210072706.3A
Other languages
Chinese (zh)
Inventor
张海威
董焕章
唐怡杰
邸庆童
郭文龙
边坤
刘赛赛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai 800 Million Spacetime Advanced Material Co ltd
Original Assignee
Shanghai 800 Million Spacetime Advanced Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai 800 Million Spacetime Advanced Material Co ltd filed Critical Shanghai 800 Million Spacetime Advanced Material Co ltd
Priority to CN202210072706.3A priority Critical patent/CN114437138A/en
Publication of CN114437138A publication Critical patent/CN114437138A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to a metal complex and an organic electroluminescent device, wherein the metal complex is a metal complex electrophosphorescent luminescent material with a condensed ring structure, and the metal complex disclosed by the invention is dark red in electroluminescence, high in luminous efficiency, good in thermal stability, easy to prepare, easy to sublimate and purify and wide in market prospect.

Description

Metal complex and organic electroluminescent device
Technical Field
The invention belongs to the technical field of organic electroluminescent display, and particularly relates to a metal complex and an organic electroluminescent device.
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 dopes octaethylporphyrin platinum in a small molecule host material of octahydroxyquinoline aluminum to prepare a red electrophosphorescent light-emitting device, so that the external quantum efficiency reaches 4%, and thus, the research on electrophosphorescence starts to get great attention from the academic world, and the research on organic electrophosphorescence is rapidly developed in the following years. 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 was almost close to 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.
The first object of the present invention is to provide a metal complex, wherein the formula of the metal complex is: 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 BDA0003482852240000021
wherein, adjacent groups W1And W2、W3And W4Each independently represents a group represented by formula (II);
Figure BDA0003482852240000031
wherein G represents O, S, CR3R4、NR5、SiR3R4Or GeR3R4Z, equal or different at each occurrence, represents CR1Or N, and ^ indication formula LACorresponding adjacent group W in (1)1And W2、W3And W4；
R1、R2、R3、R4、R5Each independently selected from one or more of hydrogen atom, deuterium atom, halogen atom, alkyl group, cycloalkyl group, heteroalkyl group, heterocycloalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, alkenyl group, cycloalkenyl group, isoalkenyl group, alkynyl group, aryl group, heteroaryl group, acyl group, carbonyl group, carboxylic acid group, ester group, nitrile group, isonitrile group, thio group, sulfonyl group, sulfinyl group, phosphino group; any adjacent substituents are optionally joined or fused to form a polycyclic ring, preferably a 5-or 6-membered ring;
wherein ring B represents an aromatic or heteroaromatic ring containing at least two carbon atoms;
LBcomprises the following steps:
Figure BDA0003482852240000032
wherein R is6、R7Each independently selected from one or more 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, a heterocyclic aryl group, an aliphatic hydrocarbon group containing nitrogen, germanium, oxygen or sulfur, a phosphine group, and a phosphinoxy 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; substituent R on ring D and ring C6、R7Is mono-or polysubstituted to saturated substitution, and R6、R7Optionally joined or fused to form a polycyclic ring, preferably a five-membered or six-membered ring;
X2、X3each independently selected from carbon or nitrogen, and X2And X3At least one is nitrogen;
LCcomprises the following steps:
Figure BDA0003482852240000033
Figure BDA0003482852240000041
wherein R is8、R9、R10Each independently selected from one or more 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 is8、R9、R10Optionally joined or fused to form a polycyclic ring, preferably a five-membered or six-membered ring.
Further, the metal M is selected from Ir or Pt.
Further, the structural formula LAOne selected from the following structures:
Figure BDA0003482852240000042
wherein G is1、G2Each independently represent O, S, CR3R4、NR5Or SiR3R4Z, equal or different at each occurrence, represents CR1Or N;
further, R1、R2、R3、R4、R5Each independently selected from one or more of hydrogen atom, deuterium atom, halogen atom, alkyl group, cycloalkyl group, heteroalkyl group, heterocycloalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, alkenyl group, cycloalkenyl group, isoalkenyl group, alkynyl group, nitrile group; any adjacent substituents are optionally joined or fused to form a multi-membered ring, preferably a five-or six-membered ring.
Further, the ring B is one or more of the following structures:
Figure BDA0003482852240000051
wherein V represents CR6R7、NR8O or S; 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 on each occurrence, CR9Or N; or two adjacent groups W represent a group of the following formula (6) or (7),
Figure BDA0003482852240000052
wherein G, Z is as defined above for G, Z and "^" represents the corresponding adjacent group W in formula (2), (3) or (5);
R6、R7、R8、R9each 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, a heterocycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, an alkenyl group, a cycloalkenyl group, and an isoalkenyl groupOne or more of alkynyl and nitrile group; any adjacent substituents are optionally joined or fused to form a multi-membered ring, preferably a five-or six-membered ring.
Further, the ring B is selected from one or more of the following structures:
Figure BDA0003482852240000053
Figure BDA0003482852240000061
wherein R is40、R41、R42Each independently selected from one or more of hydrogen atom, deuterium atom, halogen atom, cyano, chain alkyl with 1-25 carbon atoms, naphthenic base with 3-25 carbon atoms, alkoxyl with 1-25 carbon atoms, straight chain alkenyl with 2-25 carbon atoms, fluorinated alkyl with 1-25 carbon atoms, alkoxyl with 1-25 carbon atoms and straight chain alkenyl with 2-25 carbon atoms; r is40、R41、R42Each of which is mono-to saturated, and two or more adjacent groups may be optionally joined or fused to form a polycyclic ring, preferably a five-or six-membered ring.
Further, said LAIs one of LA 1-LA 270, wherein the dotted line bond represents the position coordinated with the metal M, and the specific structures of LA 1-LA 270 are as follows:
Figure BDA0003482852240000062
Figure BDA0003482852240000071
Figure BDA0003482852240000081
Figure BDA0003482852240000091
Figure BDA0003482852240000101
Figure BDA0003482852240000111
Figure BDA0003482852240000121
Figure BDA0003482852240000131
Figure BDA0003482852240000141
further, said LBIs one of LB 1-LB 220, and the specific structures of LB 1-LB 220 are as follows:
Figure BDA0003482852240000142
Figure BDA0003482852240000151
Figure BDA0003482852240000161
Figure BDA0003482852240000171
Figure BDA0003482852240000181
Figure BDA0003482852240000191
Figure BDA0003482852240000201
Figure BDA0003482852240000211
Figure BDA0003482852240000221
further, Lc is one of Lc 1-Lc 40, and the specific structures of Lc 1-Lc 40 are as follows:
Figure BDA0003482852240000222
Figure BDA0003482852240000231
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), preferably the metal complex is Ir (LAi) (LBj) (LCw), Ir (LAi)2(LBj)、Ir(LAi)3Or Ir (LAi)2(LCw)；
Wherein i is an integer of 1 to 270, j is an integer of 1 to 220, and w is an integer of 1 to 40.
In a second aspect of the present invention, there is provided an organic compoundAn electroluminescent device comprising a substrate, an anode, a cathode, a capping layer, and at least one organic layer disposed between the anode and the cathode; the material of the organic layer comprises a metal complex M (L)A)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, WO2005053051a 1.
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, preference is given to organic electroluminescent elements in which one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where 10 is-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.
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 metal complex electrophosphorescent luminescent material with a condensed ring structure, and the metal complex disclosed by the invention is dark red in electroluminescence, high in luminous efficiency, good in thermal stability, easy to prepare, easy to sublimate and purify and very wide in 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 an organic electroluminescent element device 100 of the present invention;
fig. 2 is a schematic view of an organic electroluminescent element device 200 of the present invention.
Reference numerals
In the device 100 of fig. 1, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light emitting layer, 107 is a hole blocking layer, 108 is an electron transport layer, 109 is an electron injection layer, 110 is a cathode layer, and 111 is a CPL layer.
In the device 200 of fig. 2, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light emitting layer, 107 is an electron transport layer, 108 is an electron injection layer, 109 is a cathode layer, and 110 is a CPL 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.
Example 1
Preparation of compound LA 6:
the preparation method of the ligand LA6 specifically comprises the following steps:
the first step is as follows: preparation of Compound Int-1
Figure BDA0003482852240000261
20.0mmol of 3-iodo-2-cyanobenzothiophene (CAS:2713542-25-5), 20.0mmol of o-methoxyphenylacetylene, 2.0mmol of cuprous iodide, and 0.2mmol of PdCl2(PPh3)2And (3) reacting the catalyst and 60mL of triethylamine under the protection of nitrogen for 12 hours under stirring at room temperature, filtering, concentrating the filtrate under reduced pressure, and separating and purifying by using a silica gel column to obtain a compound Int-1, namely a yellow solid, wherein the yield is as follows: 98 percent.
The second step is that: preparation of Compound Int-2
Figure BDA0003482852240000262
10.0mmol of the intermediate Int-1 prepared in the first step is dissolved in 50mL of dichloromethane, 10.0mmol of iodine is added, the reaction is stirred at room temperature for 16 hours under the protection of nitrogen, 50mL of saturated aqueous sodium thiosulfate solution is added, the organic phase is separated, dried, filtered, the filtrate is concentrated to dryness, and the filtrate is separated and purified by a silica gel column to obtain an intermediate Int-2, a white solid, and the yield is as follows: 85 percent.
The third step: preparation of compound LA6
Figure BDA0003482852240000271
15.0mmol of the intermediate Int-2 prepared in the second step is dissolved in 80mL of dry THF, the temperature is reduced to 0 ℃ under the protection of nitrogen, 18.0mmol of 3, 5-dimethylphenylmagnesium bromide THF solution is dropwise added, the mixture is stirred for reaction for 1 hour, the mixture is heated to room temperature and stirred for reaction for 1 hour, 30.0mmol of diisopropylethylamine is added, the mixture is heated to reflux and stirred for reaction for 2 hours, the mixture is cooled to room temperature, 50mL of saturated aqueous ammonium chloride solution is added, ethyl acetate is used for extraction, organic phase is dried, the filtrate is filtered, concentrated under reduced pressure and dried, and then the mixture is separated and purified by a silica gel column to obtain a compound LA6, a yellow solid, the yield: 82%, HRMS: 380.1117[ M + H]；1H-NMR(CDCl3,TMS)δ8.58(s,1H),8.46(s,1H),8.14～8.11(m,1H),7.98(s,2H),7.91～7.87(m,1H),7.79～7.74(t,1H),7.59～7.46(m,3H),7.42(s,1H),2.33(s,6H)。
Example 2
Preparation of compounds LA1 to LA5 and LA7 to LA224, referring to the preparation method of example 1, 3-iodo-2-cyanobenzofuran or 3-cyano-2-iodobenzothiophene with different substituents was substituted for 3-iodo-2-cyanobenzothiophene in the first step of example 1, o-ethynylbenzylsulfide with different substituents was substituted for o-methoxyphenylacetylene in the first step of example 1, phenylmagnesium bromide with different substituents was substituted for 3, 5-dimethylphenylmagnesium bromide in the third step of example 1, and other experimental parameters were adaptively adjusted to prepare LA1 to LA5 and LA7 to LA224 in ligand LA.
Example 3
Compound Ir (LA6)2Preparation of (LC 4):
metal complex Ir (LA6)2(LC4) a method for preparing comprising the steps of:
the first step is as follows: preparation of Compound Int-3
Figure BDA0003482852240000272
10.0mmol of the compound LA6 and 5.0mmol of IrCl3·3H2Dispersing O in 30ml of ethylene glycol ethyl ether and 10ml of water, heating and refluxing for reaction for 24 hours under the protection of nitrogen, cooling to room temperature, filtering, washing a filter cake with water, and drying in vacuum to obtain a compound Int-3, a dark brown solid, wherein the yield is as follows: 83 percent.
The second step is that: compound Ir (LA6)2Preparation of (LC4)
Figure BDA0003482852240000281
Dispersing 5.0mmol of compound Int-3 and 15.0mmol of 3, 7-diethylnonane-4, 6-dione and 25.0mmol of anhydrous potassium carbonate in 40mL of acetonitrile and 40mL of chloroform, heating under reflux for 24 hours under nitrogen protection, cooling to room temperature, pouring the reaction solution into water, extracting with dichloromethane, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, and separating and purifying the residue with silica gel column to obtain compound Ir (LA6)2(LC4), red solid, yield: 58%, HRMS: 1161.3318[ M + H]。
Example 4
Compound Ir (LA256)2Preparation of (LC 16):
metal complex Ir (LA256)2(LC16) a method for preparing comprising the steps of:
the first step is as follows: preparation of Compound Int-4
Figure BDA0003482852240000282
5.0mmol of the compound LA256 and 2.5mmol of IrCl3·3H2Dispersing O in 24ml of ethylene glycol ethyl ether and 8ml of water, heating and refluxing for reaction for 24 hours under the protection of nitrogen, cooling to room temperature, and filteringWashing the filter cake with water, and drying in vacuum to obtain a compound Int-4, a brown solid, wherein the yield is as follows: 85 percent.
The second step: compound Ir (LA256)2Preparation of (LC16)
Figure BDA0003482852240000283
Dispersing 5.0mmol of compound Int-4 and 15.0mmol of 3, 7-diethyl-3, 7-dimethyl nonane-4, 6-dione and 25.0mmol of anhydrous sodium carbonate in 40ml of acetonitrile and 40ml of chloroform, heating under reflux for 24 hours under nitrogen protection, cooling to room temperature, pouring the reaction solution into water, extracting with dichloromethane, drying the organic phase, filtering, concentrating the filtrate under reduced pressure to dryness, separating and purifying the residue with silica gel column to obtain compound Ir (LA256)2(LC16), red solid, yield: 62%, HRMS: 1191.3538[ M + H]。
Example 5
With reference to the preparation methods of example 3 and example 4, the compounds of the present invention were prepared: ir (LAi)2(LCw), i is an integer of 1 to 270, 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 6
In this example, as shown in fig. 2, in an apparatus 200, 101 is a substrate, 102 is an anode layer, 103 is a hole injection layer, 104 is a hole transport layer, 105 is an electron blocking layer, 106 is a light emitting layer, 107 is an electron transport layer, 108 is an electron injection layer, 109 is a cathode layer, 110 is a CPL layer,
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) at the above-mentioned positionThe well-arranged ITO glass substrate is arranged in a vacuum chamber and is vacuumized to 1 multiplied by 10-5～9×10-3Pa, evaporating aluminum on the ITO film to form an anode layer with a thickness of
Figure BDA0003482852240000291
Continuing to respectively evaporate a compound DNTPD as a hole injection layer with a film thickness of
Figure BDA0003482852240000292
Continuously depositing HTM on the hole injection layer film to form a hole transport layer, wherein the deposition film has a thickness of
Figure BDA0003482852240000293
(3) Continuously evaporating a layer of compound RP on the hole transport layer as an electron blocking layer, wherein the thickness of the evaporated film is
Figure BDA0003482852240000294
(4) Continuously evaporating a layer of the metal complex and the TDC of the invention on the electron barrier layer to be used as a light emitting layer of the device, wherein the TDC is a main material, the metal complex of the invention is a doping material, the doping concentration of the metal complex of the invention is 3 percent, and the thickness of the evaporated film is
Figure BDA0003482852240000295
(5) Evaporating a layer of LiQ and ET materials on the luminescent layer to be used as an electron transport layer of the device, wherein the mass ratio of LiQ to ET is 3:2, and the thickness of the evaporated film is
Figure BDA0003482852240000296
Finally, a magnesium/silver alloy layer is sequentially evaporated on the electron transport layer to be used as a cathode layer of the device, wherein the mass ratio of the magnesium/silver alloy layer is 3:7, and the thickness of the evaporated film is
Figure BDA0003482852240000297
Comparative example 1
A comparative device EL-1 was produced in the same manner as in example 6 except that the metal complex doped material of the present invention was replaced with RD-A.
The specific structures of the materials used in example 6 and comparative example 1 are shown below:
Figure BDA0003482852240000301
test examples
Devices EL-2 to EL-52 were fabricated using the different metal complexes prepared according to the present invention as doping materials according to the method of example 6, the data were normalized with EL-1 as a reference,
the roll-off ratio was calculated as follows:
roll-off ratio [1- (at a current density of 50 mA/cm)2Lower efficiency/maximum luminous efficiency)]X 100% as shown in Table 2.
TABLE 2
Figure BDA0003482852240000302
Figure BDA0003482852240000311
As can be seen from the comparison of the data in the table above, the metal complex of the invention has the advantages of low driving voltage, narrower luminous peak, good color purity and improved luminous efficiency, and the initial current density is 50mA/cm2Under these conditions, the LT 95% lifetime degradation of the device is significantly improved over the comparative device, showing a more gradual curve from the roll-off ratio data.
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 FDA0003482852230000011
wherein adjacent W1And W2、W3And W4Each independently represents a group represented by formula (II);
Figure FDA0003482852230000012
wherein G represents O, S, CR3R4、NR5、SiR3R4Or GeR3R4Z, equal or different at each occurrence, represents CR1Or N, and ^ indication formula LACorresponding adjacent group W in (1)1And W2、W3And W4；
R1、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, 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 groupOne or more of thio, sulfonyl, sulfinyl, phosphino and phosphinoxy; any adjacent substituents are optionally joined or fused to form a polycyclic ring, preferably a 5-or 6-membered ring;
wherein ring B represents an aromatic or heteroaromatic ring containing at least two carbon atoms;
LBcomprises the following steps:
Figure FDA0003482852230000021
wherein R is6、R7Each independently selected from one or more 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, a heterocyclic aryl group, an aliphatic hydrocarbon group containing nitrogen, germanium, oxygen or sulfur, a phosphine group, and a phosphinoxy 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; substituent R on ring D and ring C6、R7Is mono-or polysubstituted to saturated substitution, and R6、R7Optionally joined or fused to form a polycyclic ring, preferably a five-membered or six-membered ring;
X2、X3each independently selected from carbon or nitrogen, and X2And X3At least one is nitrogen;
LCcomprises the following steps:
Figure FDA0003482852230000022
wherein R is8、R9、R10Each independently selected from one or more 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 is8、R9、R10Optionally joined or fused to form a polycyclic ring, preferably a five-membered or six-membered 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 or 2, wherein the formula LAOne selected from the following structures:
Figure FDA0003482852230000031
wherein G is1、G2Each independently represent O, S, CR3R4、NR5Or SiR3R4Z, equal or different at each occurrence, represents CR1Or N;
R1、R2、R3、R4、R5each independently selected from one or more of hydrogen atom, deuterium atom, halogen atom, alkyl group, cycloalkyl group, heteroalkyl group, heterocycloalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, alkenyl group, cycloalkenyl group, isoalkenyl group, alkynyl group, nitrile group; any adjacent substituents are optionally joined or fused to form a multi-membered ring, preferably a five-or six-membered ring.
4. A metal complex according to any one of claims 1 to 3, wherein ring B is one or more of the following structures:
Figure FDA0003482852230000032
wherein V represents CR6R7、NR8O or S; the dashed bonds represent the positions of connection to the metal M, "-" represents the positions of connection to the ring a, and furthermore:
w at each timeIdentical or different in the occurrence is CR9Or N; or two adjacent groups W represent a group of the following formula (6) or (7),
Figure FDA0003482852230000041
wherein G, Z is as defined in claim 1 at G, Z and "^" represents the corresponding adjacent group W in formula (2), (3) or (5);
R6、R7、R8、R9each independently selected from one or more of hydrogen atom, deuterium atom, halogen atom, alkyl group, cycloalkyl group, heteroalkyl group, heterocycloalkyl group, aralkyl group, alkoxy group, aryloxy group, amino group, alkenyl group, cycloalkenyl group, isoalkenyl group, alkynyl group, nitrile group; any adjacent substituents are optionally joined or fused to form a multi-membered ring, preferably a five-or six-membered ring.
5. A metal complex according to any one of claims 1 to 4, wherein ring B is selected from one or more of the following structures:
Figure FDA0003482852230000042
Figure FDA0003482852230000051
wherein R is40、R41、R42Each independently selected from one or more of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a chain alkyl group having 1 to 25 carbon atoms in total, a cycloalkyl group having 3 to 25 carbon atoms in total, an alkoxy group having 1 to 25 carbon atoms in total, a linear alkenyl group having 2 to 25 carbon atoms in total, an alkyl group having 1 to 25 fluorinated carbon atoms in total, an alkoxy group having 1 to 25 fluorinated carbon atoms in total, and a linear alkenyl group having 2 to 25 fluorinated carbon atoms in total; r40、R41、R42Each of which is mono-substituted to saturated, and two or more adjacent groups may be optionally joined or condensed to form a five-membered ring, a six-membered ring or a seven-membered or more ring.
6. The metal complex of any one of claims 1 to 5, wherein L isAIs one of LA 1-LA 270, wherein the dotted line bond represents the position coordinated with the metal M, and the specific structures of LA 1-LA 270 are as follows:
Figure FDA0003482852230000052
Figure FDA0003482852230000061
Figure FDA0003482852230000071
Figure FDA0003482852230000081
Figure FDA0003482852230000091
Figure FDA0003482852230000101
Figure FDA0003482852230000111
Figure FDA0003482852230000121
Figure FDA0003482852230000131
7. the metal complex of any one of claims 1 to 6, wherein L isBIs one of LB 1-LB 220, and the specific structures of LB 1-LB 220 are as follows:
Figure FDA0003482852230000132
Figure FDA0003482852230000141
Figure FDA0003482852230000151
Figure FDA0003482852230000161
Figure FDA0003482852230000171
Figure FDA0003482852230000181
Figure FDA0003482852230000191
Figure FDA0003482852230000201
8. the metal complex as claimed in any one of claims 1 to 7, wherein Lc is one of LC 1-LC 40, and LC 1-LC 40 have the following specific structures:
Figure FDA0003482852230000202
Figure FDA0003482852230000211
9. the metal complex of any one of claims 1-8, 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), preferably, the metal complex is of the formula Ir (LAi) (LBj) (LCw), Ir (LAi)2(LBj)、Ir(LAi)3Or Ir (LAi)2(LCw)；
Wherein i is an integer of 1 to 270, j is an integer of 1 to 220, and w is an integer of 1 to 40.
10. An organic electroluminescent device comprising a substrate, an anode, a cathode, a capping layer, and at least one organic layer disposed between the anode and the cathode; characterized in that the material of the organic layer comprises a metal complex M (L) according to any one of claims 1 to 9A)x(LB) y (lc) z.
CN202210072706.3A 2022-01-21 2022-01-21 Metal complex and organic electroluminescent device Pending CN114437138A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210072706.3A CN114437138A (en) 2022-01-21 2022-01-21 Metal complex and organic electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210072706.3A CN114437138A (en) 2022-01-21 2022-01-21 Metal complex and organic electroluminescent device

Publications (1)

Publication Number Publication Date
CN114437138A true CN114437138A (en) 2022-05-06

Family

ID=81367134

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210072706.3A Pending CN114437138A (en) 2022-01-21 2022-01-21 Metal complex and organic electroluminescent device

Country Status (1)

Country Link
CN (1) CN114437138A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023138254A1 (en) * 2022-01-21 2023-07-27 上海八亿时空先进材料有限公司 Heterocyclic compound, and organic electroluminescent material and element

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108285459A (en) * 2017-01-09 2018-07-17 环球展览公司 Electroluminescent organic material and device
CN109608503A (en) * 2018-12-21 2019-04-12 北京诚志永华显示科技有限公司 Metal complex, electroluminescent organic material, organic electroluminescence device
CN112940048A (en) * 2021-03-01 2021-06-11 北京八亿时空液晶科技股份有限公司 Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device
CN113201027A (en) * 2021-05-20 2021-08-03 北京八亿时空液晶科技股份有限公司 Metal complex and application thereof
CN113214326A (en) * 2021-05-20 2021-08-06 北京八亿时空液晶科技股份有限公司 Metal complex, organic electroluminescent device and application
CN113292603A (en) * 2021-05-20 2021-08-24 北京八亿时空液晶科技股份有限公司 Metal complex, organic electroluminescent device and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108285459A (en) * 2017-01-09 2018-07-17 环球展览公司 Electroluminescent organic material and device
CN109608503A (en) * 2018-12-21 2019-04-12 北京诚志永华显示科技有限公司 Metal complex, electroluminescent organic material, organic electroluminescence device
CN112940048A (en) * 2021-03-01 2021-06-11 北京八亿时空液晶科技股份有限公司 Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device
CN113201027A (en) * 2021-05-20 2021-08-03 北京八亿时空液晶科技股份有限公司 Metal complex and application thereof
CN113214326A (en) * 2021-05-20 2021-08-06 北京八亿时空液晶科技股份有限公司 Metal complex, organic electroluminescent device and application
CN113292603A (en) * 2021-05-20 2021-08-24 北京八亿时空液晶科技股份有限公司 Metal complex, organic electroluminescent device and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023138254A1 (en) * 2022-01-21 2023-07-27 上海八亿时空先进材料有限公司 Heterocyclic compound, and organic electroluminescent material and element

Similar Documents

Publication Publication Date Title
JP4981252B2 (en) Electroluminescent material
WO2015087961A1 (en) Iridium complex compound, method for producing said compound, composition containing said compound, organic electroluminescent element, display device, and lighting device
CN113201027B (en) Metal complex and application thereof
JP7458483B2 (en) Metal complexes and their uses
CN109942637B (en) Metal complex and organic electroluminescent device
WO2019109886A1 (en) Organic electroluminescent compound, preparation therefor, application thereof, and electroluminescent device comprising same
CN113292603A (en) Metal complex, organic electroluminescent device and application thereof
CN112940048B (en) Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device
CN113004340B (en) Metal complex, organic electroluminescent material and organic electroluminescent element comprising same
CN114874268A (en) Organic electroluminescent material, organic electroluminescent element and consumer product
CN112175017B (en) Organic electrophosphorescent material and application thereof
CN114437138A (en) Metal complex and organic electroluminescent device
CN112979710B (en) Platinum metal complex and application thereof in organic electroluminescent device
CN115557979A (en) Boron-nitrogen hybrid compound, preparation method thereof and organic electroluminescent device
CN118005672A (en) Synthesis method of silicon-containing electron transport material
CN112175016B (en) Organic electrophosphorescent luminescent material and application thereof
CN114907179A (en) Anthracene derivative, and organic electroluminescent material, light-emitting device and consumer product using the same
CN114478650A (en) Metal complex and organic electroluminescent device containing same
CN112062753A (en) Organic compound, organic photoelectric element using same and application
CN112062772A (en) Organic compound, organic photoelectric element using same and application
CN111205273A (en) Bivalent platinum complex and preparation method and application thereof
CN112480002A (en) Organic compound containing benzoanthracene and application thereof
CN113563384B (en) Metal complex, organic electroluminescent material, light-emitting element, and electronic device
CN115322104B (en) Fluorene derivative and organic light-emitting element comprising same
CN118126093A (en) Phosphorescent metal iridium complex and organic electroluminescent device thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination