Multiple resonance metal complex and use thereof

Abstract

The present application relates to a kind of metal complex, organic electroluminescent element and consumer product, the metal complex described in the present application is used as luminescent material can obtain the red phosphor material with high luminous efficiency, and the thermal stability of the prepared luminescent material is good, the organic electroluminescent element prepared in the present application emits red phosphor, with the advantages of narrow emission spectrum, high stability and high efficiency;The electronic equipment of the present application contains the organic electroluminescent element of the present application, so as to obtain the consumer product with red electroluminescence and improved luminous efficiency.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, specifically relating to a multi-resonance metal complex, an organic electroluminescent element, and a consumer product. Background Technology

[0002] Currently, optoelectronic devices utilizing organic materials are becoming increasingly popular, and many of the materials used to manufacture these devices are relatively inexpensive, thus organic optoelectronic devices have the potential to offer a cost advantage over inorganic devices. Furthermore, the inherent properties of organic materials (such as their flexibility) make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light-emitting diodes / devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can offer performance advantages over conventional materials.

[0003] OLEDs utilize organic thin films that emit light when a voltage is applied to the device. OLEDs are becoming an increasingly popular technology for applications such as flat panel displays, lighting, and backlighting.

[0004] One application of phosphorescent emitting molecules is in full-color displays. Industry standards for such displays require pixels adapted to emit specific colors. Specifically, these standards require saturated red, green, and blue pixels. Alternatively, OLEDs can be designed to emit white light. In conventional liquid crystal displays, absorption filters are used to filter the emission from a white backlight to produce red, green, and blue emission. The same technology can be used for OLEDs. White OLEDs can be single-emitting-layer (EML) devices or stacked structures. Color can be measured using CIE coordinates, well-known in the field, but existing luminescent materials suffer from poor luminous stability and low luminous efficiency.

[0005] For the reasons stated above, this invention is proposed. Summary of the Invention

[0006] To address the aforementioned problems in the prior art, this invention provides a metal complex, an organic electroluminescent element, and a consumer product. When the metal complex of this invention is used in OLEDs, especially in the red emission region, it exhibits enhanced phosphorescence quantum yield.

[0007] The primary objective of this invention is to provide a metal complex with stable electroluminescence and high luminescence efficiency.

[0008] A second objective of the present invention is to provide an organic electroluminescent element made from the aforementioned metal complex.

[0009] A third objective of the present invention is to provide a consumer product made from the aforementioned organic electroluminescent element.

[0010] To achieve the above objectives, the present invention adopts the following technical solution:

[0011] A metal complex comprising a ligand LA of any one of formula (I), formula (II), formula (III) or formula (IV), wherein the structures of formulas I to IV are as follows:

[0012]

[0013] Among them, X 1 ~X 11 Each is independently selected from N or CR 1

[0014] Z 1 Z 2 Each can be independently represented as C or N;

[0015] Y 1 Y 2 Each is independently selected from single bonds, O, S, Se, N, and NR. 3 BR 3 BR 3 R 4 PR 3 P(O)R 3 , C=O, C=S, C=Se, C=NR 3 C = CR 3 R 4 S=O, SO2, C=R 3 CR 3 R 4 SiR 3 R 4 or GeR 3 R 4 ;

[0016] R 1 R 2 R 3 R 4 The elements selected in each occurrence, either identically or differently, are hydrogen, deuterium, fluorine, and C1–C2. 40 Alkyl chain, C3-C 40 cycloalkyl, C1-C 40 Heteroalkyl, C3-C 40 Heterocyclic alkyl, C6-C 60 Aryl alkyl, C1-C 40 Alkoxy, C6~C 60 aryloxy, amino, C3~C 40 Silyl group, C2-C 40 Alkenyl, C5-C 40 Cycloalkenyl, C3~C40 Heterene group, C2-C 40 alkynyl group, C6-C 60 Aryl, C2~C 60 heteroaryl, C1-C 40 The group consisting of acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl and phosphine groups; and any two or more adjacent substituents optionally joined or fused together to form substituted or unsubstituted five-membered rings, six-membered rings or polycycles;

[0017] The ligand LA forms a five-membered chelate ring via coordination with the metal M;

[0018] The ligand LA can be linked with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;

[0019] M is selected from one of Os, Ir, Pd, Pt, Cu, Ag and Au, preferably, M is selected from one of Ir, Pd or Pt.

[0020] Furthermore, the ligand LA is selected from the group consisting of:

[0021]

[0022]

[0023] Y 1 Selected from O, S, CR 5 R 6 or NR 5 ;

[0024] R 1 ~R 6 Each time it appears, it is selected from hydrogen, deuterium, fluorine, and C1-C2, either the same or different. 40 Alkyl chain, C3-C 40 cycloalkyl, C1-C 40 Heteroalkyl, C3-C 40 Heterocyclic alkyl, C3-C 40 Silyl, C6-C 60 Aryl, C2~C 60 A group consisting of heteroaryl and nitrile groups.

[0025] Preferably, the R 1 ~R 6 Each time it appears, it is independently selected from hydrogen, deuterium, fluorine, nitrile, and R groups. A1 ~R A55 R B1 ~R B45 R C1 ~R C295 Groups formed;

[0026] Among them, R A1 ~R A55 The structure is as follows:

[0027]

[0028] R B1 ~R B45 The structural formula is as follows:

[0029]

[0030] R C1 ~R C295 The structural formula is as follows:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] Furthermore, the metal complex has the formula Ir(LA)2(LC), where LA and LC are different from each other. The LC is:

[0040]

[0041] Among them, R, R a R b R c R d R e R f Each is independently selected from hydrogen, deuterium, fluorine, nitrile groups, C1 to C2 groups. 40 Alkyl chain, C3-C 40 cycloalkyl, C1-C 40 Heteroalkyl, C3-C 40 Heterocyclic alkyl, C3-C 40 Silyl, C6-C 60 Aryl, C2~C 60A group consisting of heteroaryl groups; and any two or more adjacent substituents are optionally joined or fused to form substituted or unsubstituted five-membered rings, six-membered rings or polycyclic rings.

[0042] Preferably, the LC is selected from the group consisting of the structures shown in LC1 to LC60, and the specific structures of LC1 to LC60 are shown below:

[0043]

[0044]

[0045] Regarding the oxidation state of metal M, when M is Ir, the oxidation state of Ir can be 3, and when M is Pt, the oxidation state of Pt can be 2.

[0046] In this invention, the terms "halogen", "halogen", "halogen atom", and "halogen group" are used interchangeably and refer to fluorine, chlorine, bromine, or iodine.

[0047] In this invention, "acyl" refers to a substituted carbonyl group (COR).

[0048] In this invention, "ester" refers to a substituted oxycarbonyl group (-OCOR or CO2R).

[0049] In this invention, "ether" refers to the -OR group.

[0050] The terms “thio group” or “thioether” used in this document are used interchangeably and refer to the -SR group.

[0051] In this invention, "sulfinyl group" refers to the -SOR group.

[0052] In this invention, "sulfonyl" refers to the -SO2R group.

[0053] In this invention, "phosphin" refers to the -PR3 group, where each R can be the same or different.

[0054] In this invention, "silyl" refers to the -SiR3 group, where each R can be the same or different.

[0055] Each of the above R is preferably selected from the group consisting of alkyl, cycloalkyl, aryl, and heteroaryl groups.

[0056] In this invention, "alkyl," "alkenyl," or "alkynyl" is preferably considered to refer to the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, penynyl, hexynyl, heptenyl, or octyynyl.

[0057] In the sense of this invention, "alkoxy" preferably refers to alkoxy groups having 1 to 40 carbon atoms, including alkoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexoxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy, and 2,2,2-trifluoroethoxy.

[0058] Generally, according to the present invention, "cycloalkyl" and "cycloalkenyl" refer to and include monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 3 to 15 cyclic carbon atoms, and may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptyl, cycloheptenyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc., wherein one or more -CH2- groups may be replaced by the above groups; in addition, one or more hydrogen atoms may be replaced by deuterium atoms, halogen atoms, or nitrile groups.

[0059] In this invention, "heteroalkyl" or "heterocyclic alkyl" refers to alkyl or cycloalkyl groups, preferably alkyl or cycloalkyl groups having 1 to 40 carbon atoms, and refers to groups in which a single hydrogen atom or -CH2- group can be substituted by oxygen, sulfur, halogen atoms, nitrogen, phosphorus, boron, silicon, or selenium, preferably groups substituted by oxygen, sulfur, or nitrogen. Furthermore, heteroalkyl or heterocyclic alkyl groups may optionally be substituted.

[0060] In this invention, "heteroalkenyl" or "heterocyclic alkenyl" refers to an alkenyl or cycloalkenyl group in which at least one carbon atom is replaced by a heteroatom. Optionally, the at least one heteroatom is selected from oxygen, sulfur, nitrogen, phosphorus, boron, silicon, or selenium, preferably oxygen, sulfur, or nitrogen. Preferred alkenyl or cycloalkenyl groups are those containing 3 to 15 carbon atoms. Furthermore, heteroalkenyl or cycloalkenyl groups may optionally be substituted.

[0061] The terms "arylalkyl" or "arylalkyl" are used interchangeably in this invention and refer to alkyl groups substituted with aryl groups. Additionally, arylalkyl groups may optionally be substituted.

[0062] According to the present invention, "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. A polycyclic system may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. Preferred aryl groups are those containing 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Particularly preferred are aryl groups having six, ten, or twelve carbon atoms. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, perylene, etc. The azurite group is preferably composed of phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may optionally be substituted.

[0063] In this invention, "heteroaryl" refers to a monocyclic aromatic group and a polycyclic aromatic ring system comprising at least one heteroatom. Heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, or selenium. In many cases, oxygen, sulfur, or nitrogen are preferred heteroatoms. A monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. A heteropolycyclic system may have two or more rings in which two atoms are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is a heteroaryl group, and other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and / or heteroaryl. A heteropolycyclic aromatic ring system may have one to six heteroatoms on each ring of the polycyclic aromatic ring system. Preferred heteroaryls are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indole-carbazole, pyridylindole, pyrrolo-dipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazol, pyridine, pyrazine, pyrimidine, pyrazine, triazine, oxazine, oxthiazine, oxadiazine, indole, benzimidazole, indazole, inoxazine, benzoxazole, benziisoxazole, benzothiazole, quinoline, isoquinoline, zoline, quinazole Phosphorus, quinoxaline, naphthidine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran-pyridine, furan-dipyridine, benzothiophene-pyridine, thiophene-dipyridine, benzoselene-pyridine, and selenophene-dipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, borazine, and their aza analogs. Additionally, the heteroaryl group may optionally be substituted.

[0064] In many cases, the substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl and phosphinyl.

[0065] As used herein, “combination of” or “group” means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that can be conceived by one of ordinary skill in the art from the applicable list. For example, alkyl and deuterium can be combined to form partially or fully deuterated alkyl groups; halogen and alkyl groups can be combined to form haloalkyl substituents, such as trifluoromethyl; and halogen, alkyl and aryl groups can be combined to form haloaralkyl groups.

[0066] In one instance, the term substitution includes a combination of two to four listed groups.

[0067] In another example, the term substitution comprises a combination of two or three groups. In yet another example, the term substitution comprises a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms that are not hydrogen or deuterium, or combinations containing up to forty atoms that are not hydrogen or deuterium, or combinations containing up to thirty atoms that are not hydrogen or deuterium. In many cases, preferred combinations of substituents will comprise up to twenty atoms that are not hydrogen or deuterium.

[0068] Furthermore, the ligand LA includes one of LA1 to LA116, and the specific structures of LA1 to LA116 are shown below:

[0069]

[0070]

[0071]

[0072]

[0073] Furthermore, the metal complex is selected from the group consisting of Ir(LAi)2(LCj), where i is an integer from 1 to 116 and j is an integer from 1 to 60; LA1 to LA116 are the structures shown above, and LC1 to LC60 are the structures shown above.

[0074] Furthermore, the metal complex Ir(LAi)2(LCj) is preferably selected from the group consisting of the following structures:

[0075]

[0076]

[0077] The organic electroluminescent material of the present invention includes one or more of the metal complexes of the present invention. The organic electroluminescent material of the present invention may be formed solely from one or more of the metal complexes of the present invention, or may contain other materials besides the metal complexes of the present invention.

[0078] By including the aforementioned metal complex of the present invention in the organic electroluminescent material of the present invention, an organic electroluminescent material with green electroluminescence and high luminous efficiency can be obtained. Furthermore, the organic electroluminescent material of the present invention is an organic electroluminescent material with good thermal stability.

[0079] An organic electroluminescent element includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer includes the aforementioned metal complex.

[0080] Furthermore, the organic layer also includes a host material comprising the group consisting of the following chemical groups: triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenene, nitrogen triphenylene, azacarbazole, azadibenzothiophene, azadibenzofuran, and azadibenzoselenene.

[0081] Any substituent in the said body is independently selected from the group consisting of the following non-fused substituents: C m H 2m+1 OC m H 2m+1 OAr 1 、N(C m H 2m+1 2. N(Ar) 1 (Ar) 2 CH=CH-C m H 2m+1 C≡CC m H 2m+1 Ar 1 Ar 1 -Ar 2 C m H 2m -Ar 1 Or without substituents, where m is an integer from 1 to 10; and where Ar 1 with Ar 2 Independently selected from the following group: benzene, biphenyl, naphthalene, triphenylene, carbazole and their heteroaromatic analogs.

[0082] In the organic electroluminescent element of the present invention, one layer may be a layer containing the metal complex of the present invention, or multiple layers may contain the metal complex of the present invention.

[0083] The organic layer can be an emission layer and the metal complex as described herein can be an emission dopant or a non-emission dopant.

[0084] A consumer product made from the aforementioned organic electroluminescent element.

[0085] The consumer products described in this invention can be one of the following: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for internal or external lighting and / or signaling, head-up displays, fully transparent or partially transparent displays, flexible displays, laser printers, telephones, cellular phones, tablet computers, tablet phones, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, microdisplays with a diagonal of less than 2 inches, 3D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screens, phototherapy devices, and signs.

[0086] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0087] The metal complexes described in this invention, by introducing boron-heteroatoms such as boron nitrogen and boron oxygen to form highly conjugated resonant rigid ligands, effectively prevent energy loss caused by bond free rotation and improve quantum efficiency. Not only does it exhibit good thermal stability, but it also increases the conjugated area, improves molecular film formation and exciton transport properties, and lowers the material's sublimation temperature. When used as luminescent materials, it can produce high-efficiency red phosphorescent materials. Electronic devices of this invention, by incorporating the organic electroluminescent element of this invention, can achieve consumer products with narrow emission spectra, high stability, and high efficiency. Attached Figure Description

[0088] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0089] Figure 1 A schematic diagram of an organic light-emitting device 100 is shown. The diagram is not necessarily drawn to scale. Device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode 109, and a capping layer (CPL) 110. Device 100 can be fabricated by sequentially depositing the described layers.

[0090] Figure 2A schematic diagram of an organic light-emitting device 200 with two light-emitting layers is shown. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 can be fabricated by sequentially depositing the described layers. Because most common OLED devices have one light-emitting layer, and device 200 has a first light-emitting layer and a second light-emitting layer, the emission peaks of the first and second light-emitting layers can be overlapping, cross-overlapping, or non-overlapping. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 Provide an example of how to add layers from the structure of device 100. Detailed Implementation

[0091] In the organic electroluminescent element of the present invention, the composition of the layers other than the layer containing the metal complex of the present invention is not limited, and those skilled in the art can determine the composition of the other layers of the organic electroluminescent element as needed based on their technical knowledge in the field.

[0092] Generally, an OLED contains at least one organic layer disposed between and electrically connected to the anode and cathode. Figure 1 A schematic diagram of an organic light-emitting device 100 is shown. The diagram is not necessarily drawn to scale. Device 100 may include a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron blocking layer 105, a light-emitting layer 106, an electron transport layer 107, an electron injection layer 108, a cathode 109, and a capping layer (CPL) 110. Device 100 can be fabricated by sequentially depositing the described layers.

[0093] Figure 2 A schematic diagram of an organic light-emitting device 200 containing two light-emitting layers is shown. The device includes a substrate 201, an anode 202, a hole injection layer 203, a hole transport layer 204, a first light-emitting layer 205, an electron transport layer 206, a charge generation layer 207, a hole injection layer 208, a hole transport layer 209, a second light-emitting layer 210, an electron transport layer 211, an electron injection layer 212, and a cathode 213. The device 200 can be fabricated by sequentially depositing the described layers. Because the most common OLED devices have one monochromatic light-emitting layer or three light-emitting layers with three primary colors, device 200 has two light-emitting layers of the same color. Materials similar to those described with respect to device 100 can be used in the corresponding layers of device 200. Figure 2 Provide an example of how to add layers from the structure of device 100.

[0094] Figure 1 and Figure 2 The simple layered structures described herein are provided as non-limiting examples, and it should be understood that embodiments of the invention can be used in combination with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures can be used. A functional OLED can be realized by combining the described layers in different ways based on design, performance, and cost factors, or several layers can be omitted entirely. Other layers not specifically described may also be included. Materials different from those specifically described may be used. Although many examples provided herein describe various layers as comprising a single material, it will be understood that combinations of materials, such as mixtures of matrix and dopant, or more generally, mixtures, can be used. Furthermore, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 204 transports holes and injects holes into light-emitting layer 205, and can be described as a hole transport layer or an electron blocking layer. In one embodiment, the OLED can be described as having an organic layer disposed between a cathode and an anode. This organic layer may comprise a single layer or may further comprise, as exemplified... Figure 1 and Figure 2 Multiple layers of different organic materials are described.

[0095] Structures and materials not specifically described can also be used, such as PLEDs containing polymer materials. As another example, OLEDs with a single organic layer or multiple stacks can be used. OLED structures can be detached from... Figure 1 and Figure 2 The simple layered structure is illustrated in the diagram. For example, the substrate may include angled reflective surfaces to improve optical coupling.

[0096] Unless otherwise specified, any of the layers in the various embodiments can be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, organic vapor deposition methods, or applying one or more layers by means of carrier gas sublimation, wherein, in 10- 5 The material is applied at a pressure between millibar and 1 bar. A particular example of this method is an organic vapor jet printing method, in which the material is applied directly through a nozzle and is therefore structured. Other suitable deposition methods include producing one or more layers, for example by spin coating, or by means of any desired printing method such as screen printing, flexographic printing, offset printing, photoinitiated thermal imaging, thermal transfer, inkjet printing, or nozzle printing. Soluble compounds, for example, are obtained through appropriate substitution. These methods are also particularly suitable for oligomers, dendritic macromolecules, and polymers. Furthermore, mixing methods are feasible, in which one or more layers are applied, for example, from a solution and one or more additional layers are applied by vapor phase deposition.

[0097] The device manufactured according to embodiments of the present invention may optionally further include a capping layer, also called a barrier layer. One use of the capping layer is to protect the electrodes and organic layers from damage caused by exposure to harmful substances in the environment, including moisture, vapor, and / or gases. The capping layer may be deposited on, under, or beside a substrate or electrode, or on any other part of the device, including edges. The capping layer may comprise a single layer or multiple layers. The capping layer can be formed using various known chemical vapor deposition techniques and may comprise compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the capping layer. The capping layer may incorporate inorganic or organic compounds, or both. Preferably, the capping layer comprises a mixture of polymeric and non-polymeric materials. For it to be considered a mixture, the aforementioned polymeric and non-polymeric materials constituting the capping layer should be deposited under the same conditions and / or simultaneously. The weight ratio of the polymeric material to the non-polymeric material may be in the range of 95 / 5 to 5 / 95. In one instance, the mixture of polymeric and nonpolymeric materials is essentially composed of polymeric silicon and inorganic silicon.

[0098] In any of the compounds mentioned above used in each layer of the OLED device described above, hydrogen atoms may be partially or fully deuterated. Therefore, any specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, etc., may be in their undeuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., (but not limited to) alkyl, aryl, cycloalkyl, heteroaryl, etc.) may also be in their undeuterated, partially deuterated, and fully deuterated forms.

[0099] The materials and structures described herein can be applied to devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors can use the materials and structures. Furthermore, organic devices such as organic transistors can use the materials and structures.

[0100] These methods are generally known to those skilled in the art, and they can be applied to organic electroluminescent devices containing compounds according to the present invention without any inventive effort.

[0101] According to one embodiment, novel ligands for metal complexes are disclosed. The inventors have discovered that the introduction of these ligands unexpectedly narrows the emission spectrum, lowers the sublimation temperature, and improves the luminescence efficiency of the device.

[0102] As a method for preparing the organic electroluminescent element of the present invention, the following preparation methods can be listed, but are not limited thereto, and those skilled in the art can make various modifications based on common technical knowledge in the field. The aforementioned preparation method includes the following steps:

[0103] Cleaning process: Clean the glass substrate containing ITO using cleaning agents, deionized water, organic solvents, etc.

[0104] The process of forming a hole injection layer: A hole injection layer forming material containing the metal complex of the present invention is deposited on the aforementioned anode layer by vacuum evaporation, thereby forming a hole injection layer containing the metal complex of the present invention on the aforementioned substrate;

[0105] The process of forming the hole transport layer: The hole transport layer is formed on the aforementioned hole injection layer by vacuum evaporation;

[0106] The process of forming an organic light-emitting layer: an organic light-emitting layer forming material containing the material of the present invention is formed on the aforementioned hole transport layer by vacuum evaporation;

[0107] The process of forming an electron transport layer: an electron transport layer forming material containing the metal complex of the present invention is formed on the aforementioned organic light-emitting layer by vacuum evaporation.

[0108] The process of forming the cathode layer involves depositing, sputtering, or spin-coating a cathode forming material onto the aforementioned electron transport layer to form the cathode layer.

[0109] In the embodiments of the present invention, the performance testing conditions of the prepared electroluminescent device are as follows:

[0110] Luminosity and chromaticity coordinates: tested using a PhotoResearch PR-715 spectral scanner;

[0111] Current density and turn-on voltage: tested using a Keithley 2420 digital source meter;

[0112] Power efficiency: Tested using NEWPORT 1931-C;

[0113] Life test: The LTS-1004AC life test device was used.

[0114] Example

[0115] This invention also discloses a method for synthesizing the metal complex Ir(LAi)2(LCj), comprising the following steps:

[0116] Step 1: Preparation of iridium chloride coordination intermediate

[0117]

[0118] 10.0 mmol of compound LAI and 5.0 mmol of IrCl3·3H2O were dispersed in 30 mL of ethylene glycol ethyl ether and 10 mL of water. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water and dried under vacuum to obtain the iridium chloride coordination intermediate, which could be used directly in the next step of preparation without purification.

[0119] Step 2: Preparation of the metal complex Ir(LAi)2(LCj)

[0120]

[0121] 5.0 mmol of iridium chloride coordination intermediate, 15.0 mmol of LCj, and 25.0 mmol of anhydrous potassium carbonate or anhydrous sodium carbonate were dispersed in 40 mL of acetonitrile and 40 mL of chloroform. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, poured into water, extracted with dichloromethane, dried the organic phase, filtered, concentrated the filtrate under reduced pressure, and purified the residue by silica gel column chromatography to obtain compound Ir(LAi)2(LCj).

[0122] Where i is an integer from 1 to 116, and j is an integer from 1 to 60.

[0123] Example 1

[0124] The following examples, using ligands LA8 and LC11 as representative embodiments, illustrate the preparation of the metal complex PTO2. The preparation of the metal complex of this invention includes the following steps:

[0125] Step 1: Preparation of compound Int-1

[0126]

[0127] 20.0 mmol of SM-0, 22.0 mmol of 2-fluorobromobenzene, and 30.0 mmol of cesium carbonate were dissolved in 50 mL of DMF. Under nitrogen protection, the mixture was heated to 150 °C and stirred for 5 hours. After cooling to room temperature, 250 mL of ice-water solution was added, and the mixture was stirred for 30 minutes. The mixture was extracted with ethyl acetate, washed with water, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was then purified by silica gel column chromatography to give compound Int-1 as a yellow solid with a yield of 85%.

[0128] Step 2: Preparation of compound Int-2

[0129]

[0130] 20.0 mmol of Int-1 was dissolved in 80 mL of N,N-dimethylaniline. Under nitrogen protection, the solution was cooled to -78 °C, and 30.0 mmol of 2.5 M n-butyllithium n-hexyl solution was added dropwise. The mixture was stirred for 30 minutes, followed by the addition of 22.0 mmol of boron tribromide. The mixture was stirred for 1 hour, then heated to 155 °C and stirred for 12 hours. The mixture was cooled to room temperature, and 250 mL of water was added dropwise. The mixture was extracted with ethyl acetate, and the organic phase was separated and washed three times with saturated brine. The organic phase was collected, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was purified by silica gel column chromatography to give compound LA8 as a yellow solid with a yield of 42%.

[0131] Step 3: Preparation of iridium chloride coordination intermediate

[0132]

[0133] 10.0 mmol of compound LA8 and 5.0 mmol of IrCl3·3H2O were dispersed in 30 mL of ethylene glycol ethyl ether and 10 mL of water. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water and dried under vacuum to obtain iridium chloride coordination intermediate, a red solid, which could be used directly for the next step of preparation without purification.

[0134] Step 4: Preparation of metal complex PTO2

[0135]

[0136] 5.0 mmol of iridium chloride coordination intermediate, 15.0 mmol of LC11, and 25.0 mmol of anhydrous sodium carbonate were dispersed in 40 mL of acetonitrile and 40 mL of chloroform. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, and the reaction solution was poured into water. The solution was extracted with dichloromethane, dried over the organic phase, filtered, and the filtrate was concentrated to dryness under reduced pressure. The residue was purified by silica gel column chromatography to give compound PTO2 as a red solid; yield 32%. MS (MALDI-TOF): m / z 1139.0616 [M+H] + .

[0137] Example 2

[0138] The following examples, using ligands LA71 and LC4 as representative examples, illustrate the preparation of the metal complex Ir(LA71)2(LC4). The preparation of the metal complex of this invention includes the following steps:

[0139] Step 1: Preparation of compound Int-3

[0140]

[0141] 20.0 mmol of SM-1, 22.0 mmol of 2-fluorobromobenzene, and 30.0 mmol of potassium carbonate were dissolved in 50 mL of DMF. Under nitrogen protection, the mixture was heated to 150 °C and stirred for 12 hours. After cooling to room temperature, 250 mL of ice-water solution was added, and the mixture was stirred for 30 minutes. The mixture was extracted with ethyl acetate, washed with saturated brine, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was then purified by silica gel column chromatography to give compound Int-3 as a yellow solid with a yield of 87%.

[0142] Step 2: Preparation of compound LA71

[0143]

[0144] Under nitrogen protection, 15.0 mmol of intermediate Int-3 was dissolved in 50 mL of dry xylene, cooled to -78°C with liquid nitrogen, and 24.0 mL of 2.5 M n-butyllithium hexane solution was slowly added dropwise. The mixture was stirred for 30 minutes, and then 22.5 mmol of boron tribromide was slowly added dropwise. The mixture was stirred for 1 hour, the liquid nitrogen bath was removed, and then 22.5 mmol of N,N-diisopropylethylamine was slowly added dropwise. The mixture was heated to room temperature and stirred for 1 hour, then heated to reflux and stirred for 15 hours. After cooling to room temperature, 150 mL of 0.5 M sodium acetate aqueous solution was added, and the mixture was extracted with ethyl acetate. The organic phase was collected, dried, concentrated under reduced pressure to dryness, and then purified by silica gel column chromatography to give compound LA71 as a white solid in 47% yield.

[0145] Step 3: Preparation of iridium chloride coordination intermediate

[0146]

[0147] 10.0 mmol of compound LA71 and 5.0 mmol of IrCl3·3H2O were dispersed in 30 mL of ethylene glycol ethyl ether and 10 mL of water. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water and dried under vacuum to obtain the iridium chloride coordination intermediate, which was a red solid and could be used directly for the next step of preparation without purification.

[0148] Step 4: Preparation of the metal complex Ir(LA71)2(LC4)

[0149]

[0150] 5.0 mmol of iridium chloride coordination intermediate, 15.0 mmol of LC4, and 25.0 mmol of anhydrous sodium carbonate were dispersed in 40 mL of acetonitrile and 40 mL of chloroform. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, and the reaction solution was poured into water. The solution was extracted with dichloromethane, dried over the organic phase, filtered, and the filtrate was concentrated to dryness under reduced pressure. The residue was purified by silica gel column chromatography to give compound Ir(LA71)2 (LC4), a red solid; yield 37%, MS (MALDI-TOF): m / z 1153.0864 [M+H]. + .

[0151] Example 3

[0152] The preparation of the metal complex PT23 includes the following steps:

[0153] Step 1: Preparation of compound Int-4

[0154]

[0155] Under nitrogen protection, 21.0 mmol of 8-bromonaphthalene-1-boronic acid (CAS: 167105-03-5) and 20.0 mmol of 4-chloro-6-phenoxypyrimidine (CAS: 124041-00-5) were dissolved in 80 mL of toluene. Then, 40.0 mmol of potassium phosphate hydrate, 0.2 mmol of Pd(PPh3)4, 50 mL of ethanol and 30 mL of water were added. The mixture was heated to reflux and stirred for 12 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, washed with water, dried, filtered, and the filtrate was concentrated to dryness under reduced pressure. The filtrate was then purified by silica gel column chromatography to give compound Int-4 in 58% yield.

[0156] Step 2: Preparation of compound Int-5

[0157]

[0158] Under nitrogen protection, 15.0 mmol of intermediate Int-4 was dissolved in 50 mL of dry xylene. The solution was cooled to -78 °C with liquid nitrogen, and 24.0 mL of 2.5 M n-butyllithium hexane solution was slowly added dropwise. The mixture was stirred for 30 minutes, and then 22.5 mmol of boron tribromide was slowly added dropwise. The mixture was stirred for 1 hour, the liquid nitrogen bath was removed, and then 22.5 mmol of triethylamine was slowly added dropwise. The mixture was heated to room temperature and stirred for 1 hour, then heated to reflux and stirred for 15 hours. The mixture was cooled to room temperature, and then 150 mL of 0.5 M sodium acetate aqueous solution was added. The mixture was extracted with ethyl acetate, the organic phase was collected, dried, concentrated under reduced pressure to dryness, and then purified by silica gel column chromatography to give compound Int-5 as a yellow solid in 52% yield.

[0159] Step 3: Preparation of iridium chloride coordination intermediate

[0160]

[0161] 10.0 mmol of compound Int-5 and 5.0 mmol of IrCl3·3H2O were dispersed in 30 mL of ethylene glycol ethyl ether and 10 mL of water. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, filtered, the filter cake was washed with water and dried under vacuum to obtain the iridium chloride coordination intermediate, which was a red solid and could be used directly for the next step of preparation without purification.

[0162] Step 4: Preparation of metal complex PT23

[0163]

[0164] 5.0 mmol of iridium chloride coordination intermediate, 15.0 mmol of LC11, and 25.0 mmol of anhydrous potassium carbonate were dispersed in 60 mL of ethylene glycol diethyl ether. The mixture was refluxed under nitrogen protection for 24 hours, cooled to room temperature, and the reaction solution was poured into water. The mixture was filtered, and the filter cake was washed with water and ethanol. The solid was purified by silica gel column chromatography to give compound PT23 as a red solid; yield 38%. MS (MALDI-TOF): m / z 1029.3326 [M+H] + .

[0165] Following the synthesis method described in the above embodiments, a metal complex, Ir(LAi)2(LCj), was prepared; where i is an integer from 1 to 116 and j is an integer from 1 to 60.

[0166] Using only ligand LC11 as a representative of LCj, metal complexes were prepared: PTO1, PTO3~PT22, PT24~PT48.

[0167] Example 4: Fabrication of Organic Electroluminescent Element

[0168] The glass substrate coated with the ITO conductive layer was ultrasonically treated in a cleaning agent for 30 minutes, rinsed in deionized water, ultrasonically treated in an acetone / ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dry, irradiated with a UV cleaner for 10 minutes, and bombarded with a low-energy cation beam.

[0169] The prepared ITO glass substrate was placed in a vacuum chamber and evacuated to a vacuum level of less than 1 × 10⁻⁶. -5 Pa, a layer of metallic silver is deposited on the above ITO film as an anode layer, and the thickness of the deposited film is [missing information]. Continue by depositing compounds HIO2 and F4TCNQ as hole injection layers, respectively, where F4TCNQ accounts for 3% of the mass of HIO2, and the deposited film thickness is... HTM is then deposited onto the aforementioned hole injection layer to form a hole transport layer, with a deposition thickness of [missing information].

[0170] EBM was deposited as an electron blocking layer on the aforementioned hole transport layer, with a deposition thickness of [missing information].

[0171] An organic light-emitting layer is deposited on the aforementioned electron blocking layer. The light-emitting layer contains H1 as the main component and 3% by mass of the metal complex prepared in this invention as a dopant material. The thickness of the deposited film is...

[0172] On the aforementioned organic light-emitting layer, an electron transport layer consisting of LiQ and ETM is deposited by vapor deposition, wherein the LiQ content is 50% of the mass of the ETM, and the deposited film thickness is [missing information].

[0173] A further layer of LiF is deposited on the aforementioned light-emitting layer as the electron injection layer of the device, with a deposition thickness of [missing information].

[0174] Magnesium and silver are deposited as the cathode layer of the element on top of the aforementioned electron injection layer, wherein the mass ratio of magnesium to silver is 1:2, and the thickness of the deposited film is [missing information].

[0175] Finally, an NPB layer is deposited on top of the transparent cathode as the CPL layer for the device, with a deposition thickness of [missing information]. The OLED element provided by this invention is obtained.

[0176] The structural formulas of the aforementioned HI02, HTM, EBM, H1, LiQ, F4TCNQ, and ETM are shown below:

[0177]

[0178] Comparative Example 1

[0179] The metal complex of the present invention shown in Example 4 was replaced with the compound shown in RD-1, and the other steps were the same as in Example 4 to prepare comparative element 1.

[0180] The structure of RD-1 is as follows:

[0181]

[0182] Comparative Example 2

[0183] The compound shown in RD-2 was used instead of the metal complex of the present invention in Example 4, and the other steps were the same as in Example 4 to prepare comparative element 2.

[0184] The structure of RD-2 is as follows:

[0185]

[0186] Comparative Example 3

[0187] The metal complex of the present invention shown in Example 4 was replaced with the compound shown in RD-3, and the other steps were the same as in Example 4 to prepare the comparative element 3.

[0188] The structure of RD-3 is as follows:

[0189]

[0190] The organic electroluminescent elements prepared by the above process were subjected to the following performance tests:

[0191] The driving voltage, current efficiency, and lifetime of the organic electroluminescent elements prepared in Example 4 and Comparative Examples 1, 2, and 3 were determined using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the measurement was performed when the current density of the organic electroluminescent element reached 10 mA / cm². 2 The voltage at that time is the driving voltage, and the brightness at that time is measured simultaneously; the ratio of brightness to current density is the current efficiency; the LT95% lifespan test is as follows: using a luminance meter at 1000 cd / m² 2 At a constant current under the given brightness, the brightness decay of the organic electroluminescent element was measured to be 950 cd / m². 2 The time is in hours. *The data is normalized relative to Comparison Element 1, where the data in parentheses is the test data. See Table 1 for data details.

[0192] Table 1

[0193]

[0194]

[0195]

[0196] As can be seen from Table 1, the metal complex of the present invention, as a doping material for the light-emitting layer, has a lower driving voltage than the comparative device, and in particular, it has a significant advantage in external quantum efficiency and LT95% lifetime. This indicates that the metal complex of the present invention has good light emission color purity and is a high-performance doping material for the light-emitting layer.

[0197] Table 1 above only lists the properties of some metal complexes. The inventors also conducted the above tests on other metal complexes, and the results were basically the same. Due to space limitations, they will not be listed one by one.

[0198] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention. The above descriptions are merely specific embodiments of this invention, but the scope of protection of this invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in this invention should be included within the scope of protection of this invention. Therefore, the scope of protection of this invention should be determined by the scope of the claims.

Claims

1. A metal complex, characterized in that, The metal complex has the formula Ir(LA)2(LC), wherein the ligand LA is selected from the group consisting of: ； The LC is selected from the structure shown in LC4 or LC11 below: Among them, Y 1 Selected from O or S; The R 1 ~R 3 Each time it appears, it is independently selected from hydrogen, deuterium, fluorine, and C1~C. 40 Alkyl chain, C3~C 40 Groups consisting of cycloalkyl groups.

2. The metal complex according to claim 1, characterized in that, The ligand LA includes one of the following structures:

3. The metal complex according to claim 2, characterized in that, The metal complex is selected from the group consisting of the following structures:

4. An organic electroluminescent element, comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, characterized in that, The organic layer comprises the metal complex as described in claim 1 or 2.

5. A consumer product comprising the organic electroluminescent element of claim 4.

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