Patent Application
20230203075
This application claims priority from Korean Patent Application No. 10-2021-0188298 filed on Dec. 27, 2021 in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. 119, the contents of which in its entirety are herein incorporated by reference.
The present disclosure relates to an organometallic compound, and more particularly, to an organometallic compound having phosphorescent properties and an organic light-emitting diode including the same.
As a display device is applied to various fields, interest with the display device is increasing. One of the display devices is an organic light-emitting display device including an organic light-emitting diode (OLED) which is rapidly developing.
In the organic light-emitting diode, when electric charges are injected into a light-emitting layer formed between a positive electrode and a negative electrode, an electron and a hole are recombined with each other in the light-emitting layer to form an exciton and thus energy of the exciton is converted to light. Thus, the organic light-emitting diode emits the light. Compared to conventional display devices, the organic light-emitting diode may operate at a low voltage, consume relatively little power, render excellent colors, and may be used in a variety of ways because a flexible substrate may be applied thereto. Further, a size of the organic light-emitting diode may be freely adjustable.
The organic light-emitting diode (OLED) has superior viewing angle and contrast ratio compared to a liquid crystal display (LCD), and is lightweight and is ultra-thin because the OLED does not require a backlight. The organic light-emitting diode includes a plurality of organic layers between a negative electrode (electron injection electrode; cathode) and a positive electrode (hole injection electrode; anode). The plurality of organic layers may include a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron blocking layer, and a light-emitting layer, an electron transport layer, etc.
In this organic light-emitting diode structure, when a voltage is applied across the two electrodes, electrons and holes are injected from the negative and positive electrodes, respectively, into the light-emitting layer and thus excitons are generated in the light-emitting layer and then fall to a ground state to emit light.
Organic materials used in the organic light-emitting diode may be largely classified into light-emitting materials and charge-transporting materials. The light-emitting material is an important factor determining luminous efficiency of the organic light-emitting diode. The luminescent material have high quantum efficiency, excellent electron and hole mobility, and exist uniformly and stably in the light-emitting layer. The light-emitting materials may be classified into light-emitting materials emitting light of blue, red, and green colors based on colors of the light. A color-generating material may include a host and dopants to increase the color purity and luminous efficiency through energy transfer.
In recent years, there is a trend to use phosphorescent materials rather than fluorescent materials for the light-emitting layer. When the fluorescent material is used, singlets as about 25% of excitons generated in the light-emitting layer are used to emit light, while most of triplets as 75% of the excitons generated in the light-emitting layer are dissipated as heat. However, when the phosphorescent material is used, singlets and triplets are used to emit light.
Conventionally, an organometallic compound is used as the phosphorescent material used in the organic light-emitting diode. Research and development of the phosphorescent material to solve low efficiency and lifetime problems are continuously required.
Accordingly, a purpose of the present invention is to provide an organometallic compound capable of lowering operation voltage, and improving efficiency and lifespan, and an organic light-emitting diode including an organic light-emitting layer containing the same.
Purposes of the present disclosure are not limited to the above-mentioned purpose. Other purposes and advantages of the present disclosure that are not mentioned may be understood based on following descriptions, and may be more clearly understood based on example embodiments of the present disclosure. Further, it will be easily understood that the purposes and advantages of the present disclosure may be realized using means shown in the claims and combinations thereof.
In order to achieve the above purpose, the present disclosure provides an organometallic compound having a novel structure represented by following Chemical Formula 1, an organic light-emitting diode in which a light-emitting layer contains the same as dopants thereof, and an organic light-emitting display device including the organic light-emitting diode:
Ir(LA)m(LB)n [Chemical Formula 1]
wherein in Chemical Formula 1,
LA may be represented by one selected from a group consisting of following Chemical Formula 2-1 to Chemical Formula 2-6,
LB may be a bidentate ligand represented by following Chemical Formula 3,
m may be 1, 2 or 3, n may be 0, 1 or 2, and a sum of m and n may be 3,
wherein in each of Chemical Formula 2-1 to Chemical Formula 2-6,
X may represent one selected from a group consisting of —CH2—, oxygen, —NH— and sulfur,
each of R1-1, R1-2, R1-3, R1-4, R2-1, R2-2, R3-1, R3-2, R4-1 and R4-2 may independently represent one selected from a group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
optionally, two adjacent functional groups among R1-1, R1-2, R1-3, R1-4, R2-1, R2-2, R3-1, R3-2, R4-1 and R4-2 may bind to each other to form a ring structure.
The organometallic compound according to example embodiments of the present disclosure may be used as the dopant of the phosphorescent light-emitting layer of the organic light-emitting diode, such that the operation voltage of the organic light-emitting diode may be lowered, and the efficiency and lifespan characteristics of the organic light-emitting diode may be improved.
Effects of the present disclosure are not limited to the above-mentioned effects, and other effects as not mentioned will be clearly understood by those skilled in the art from following descriptions.
It is to be understood that both the foregoing general description and the following detailed description of the present disclosure are exemplary and explanatory and are intended to provide further explanation of the inventive concepts as claimed.
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this application, illustrate embodiments of the disclosure and together with the description serve to explain principles of the disclosure.
Advantages and features of the present disclosure, and a method of achieving the advantages and features will become apparent with reference to example embodiments described later in detail together with the accompanying drawings. However, the present disclosure is not limited to the example embodiments as disclosed below, but may be implemented in various different forms. Thus, these example embodiments are set forth only to make the present disclosure complete, and to completely inform the scope of the present disclosure to those of ordinary skill in the technical field to which the present disclosure belongs, and the present disclosure is only defined by the scope of the claims.
A shape, a size, a ratio, an angle, a number, etc. disclosed in the drawings for describing the example embodiments of the present disclosure are illustrative, and the present disclosure is not limited thereto. The same reference numerals refer to the same elements herein. Further, descriptions and details of well-known steps and elements are omitted for simplicity of the description. Furthermore, in the following detailed description of the present disclosure, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be understood that the present disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail so as not to unnecessarily obscure aspects of the present disclosure.
The terminology used herein is directed to the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular constitutes “a” and “an” are intended to include the plural constitutes as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprise”, “comprising”, “include”, and “including” when used in this specification, specify the presence of the stated features, integers, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, operations, elements, components, and/or portions thereof. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expression such as “at least one of” when preceding a list of elements may modify the entire list of elements and may not modify the individual elements of the list. In interpretation of numerical values, an error or tolerance therein may occur even when there is no explicit description thereof.
In addition, it will also be understood that when a first element or layer is referred to as being present “on” a second element or layer, the first element may be disposed directly on the second element or may be disposed indirectly on the second element with a third element or layer being disposed between the first and second elements or layers. It will be understood that when an element or layer is referred to as being “connected to”, or “coupled to” another element or layer, it may be directly on, connected to, or coupled to the other element or layer, or one or more intervening elements or layers may be present. In addition, it will also be understood that when an element or layer is referred to as being “between” two elements or layers, it may be the only element or layer between the two elements or layers, or one or more intervening elements or layers may also be present.
Further, as used herein, when a layer, film, region, plate, or the like is disposed “on” or “on a top” of another layer, film, region, plate, or the like, the former may directly contact the latter or still another layer, film, region, plate, or the like may be disposed between the former and the latter. As used herein, when a layer, film, region, plate, or the like is directly disposed “on” or “on a top” of another layer, film, region, plate, or the like, the former directly contacts the latter and still another layer, film, region, plate, or the like is not disposed between the former and the latter. Further, as used herein, when a layer, film, region, plate, or the like is disposed “below” or “under” another layer, film, region, plate, or the like, the former may directly contact the latter or still another layer, film, region, plate, or the like may be disposed between the former and the latter. As used herein, when a layer, film, region, plate, or the like is directly disposed “below” or “under” another layer, film, region, plate, or the like, the former directly contacts the latter and still another layer, film, region, plate, or the like is not disposed between the former and the latter.
In descriptions of temporal relationships, for example, temporal precedent relationships between two events such as “after”, “subsequent to”, “before”, etc., another event may occur therebetween unless “directly after”, “directly subsequent” or “directly before” is indicated.
It will be understood that, although the terms “first”, “second”, “third”, and so on may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section described below could be termed a second element, component, region, layer or section, without departing from the spirit and scope of the present disclosure.
The features of the various embodiments of the present disclosure may be partially or entirely combined with each other, and may be technically associated with each other or operate with each other. The example embodiments of the present disclosure may be implemented independently of each other and may be implemented together in an association relationship.
In interpreting a numerical value, the value is interpreted as including an error range unless there is no separate explicit description thereof.
It will be understood that when an element or layer is referred to as being “connected to”, or “coupled to” another element or layer, it may be directly on, connected to, or coupled to the other element or layer, or one or more intervening elements or layers may be present. In addition, it will also be understood that when an element or layer is referred to as being “between” two elements or layers, it may be the only element or layer between the two elements or layers, or one or more intervening elements or layers may also be present.
The features of the various embodiments of the present disclosure may be partially or entirely combined with each other, and may be technically associated with each other or operate with each other. The example embodiments of the present disclosure may be implemented independently of each other and may be implemented together in an association relationship.
Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
As used herein, a phrase “adjacent functional groups bind to each other to form a ring structure” means that adjacent functional groups may bind to each other to form a substituted or unsubstituted alicyclic ring structure (cycloalkyl group), a substituted or unsubstituted aromatic ring structure (aryl group), or a ring structure (alkylaryl group or arylalkyl group) having both substituted or unsubstituted aliphatic and aromatic rings. A phrase “adjacent functional group” to a certain functional group may mean a functional group replacing an atom directly connected to an atom which the certain functional group replaces, a functional group that is sterically closest to the certain functional group, or a functional group replacing an atom replaced with the certain functional group. For example, two functional groups replacing an ortho position in a benzene ring structure and two functional groups replacing the same carbon in an aliphatic ring may be interpreted as “adjacent functional groups.”
As used herein and unless otherwise indicated, the term “substituted,” means that the specified group or moiety bears one or more substituents. The term “unsubstituted,” means that the specified group bears no substituents.
As used herein and unless otherwise indicated, the term “substituent” means a non-hydrogen moiety, for example, deuterium, hydroxy, halogen (e.g. fluoro, chloro or bromo), carboxy, carboxamido, imino, alkanoyl, cyano, cyanomethyl, nitro, amino, alkyl, alkenyl, alkynyl, cycloalkyl, arylalkyl, aryl, heterocycle, heteroaryl, hydroxyl, amino, alkoxy, halogen, carboxy, carbalkoxy, carboxamido, monoalkylaminosulfmyl, dialkylaminosulfmyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonylamino, hydroxysulfonyloxy, alkoxysulfonyloxy, alkylsulfonyloxy, hydroxysulfonyl, alkoxysulfonyl, alkylsulfonylalkyl, monoalkylaminosulfonylalkyl, dialkylaminosulfonylalkyl, monoalkylaminosulfmylalkyl, dialkylaminosulfmylalkyl and the like.
As used herein and unless otherwise indicated, the term “alkyl” means a substituted or unsubstituted, saturated, linear or branched hydrocarbon chain radical. Examples of alkyl groups include, but are not limited to, C1-C15 linear, branched or cyclic alkyl, such as methyl, ethyl, propyl, isopropyl, cyclopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, isobutyl, sec-butyl, t-butyl, cyclobutyl, pentyl, isopentyl, neopentyl, hexyl, and cyclohexyl and longer alkyl groups, such as heptyl, octyl, nonyl and decyl. An alkyl can be unsubstituted or substituted with one or two suitable substituents.
As used herein and unless otherwise specified the term “cycloalkyl” means a monocyclic or polycyclic saturated ring comprising carbon and hydrogen atoms and having no carbon-carbon multiple bonds. A cycloalkyl group can be unsubstituted or substituted. Examples of cycloalkyl groups include, but are not limited to, (C3-C7)cycloalkyl groups, including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, and saturated cyclic and bicyclic terpenes. A cycloalkyl group can be unsubstituted or substituted. Preferably, the cycloalkyl group is a monocyclic ring or bicyclic ring.
As used herein and unless otherwise indicated, the term “aryl” means a monocyclic or polycyclic conjugated ring structure that is well known in the art. Examples of suitable aryl groups or aromatic rings include, but are not limited to, phenyl, tolyl, anthacenyl, fluorenyl, indenyl, azulenyl, and naphthyl. An aryl group can be unsubstituted or substituted with one or two suitable substituents.
As used herein and unless otherwise indicated, the term “substituted aryl” includes an aryl group optionally substituted with one or more functional groups, such as halo, alkyl, haloalkyl (e g., trifluoromethyl), alkoxy, haloalkoxy (e.g., difluoromethoxy), alkenyl, alkynyl, aryl, heteroaryl, arylalkyl, aryloxy, aryloxyalkyl, arylalkoxy, alkoxycarbonyl, alkylcarbonyl, arylcarbonyl, arylalkenyl, aminocarbonylaryl, arylthio, arylsulfmyl, arylazo, heteroarylalkyl, heteroaryl alkenyl, heteroaryloxy, hydroxy, nitro, cyano, amino, substituted amino wherein the amino includes 1 or 2 substituents (which are optionally substituted alkyl, aryl or any of the other substituents recited herein), thiol, alkylthio, arylthio, heteroarylthio, arylthioalkyl, alkoxyarylthio, alkylaminocarbonyl, arylaminocarbonyl, aminocarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkylcarbonylamino, arylcarbonylamino, arylsulfmyl, arylsulfmylalkyl, arylsulfonylamino, or arylsulfonaminocarbonyl and/or any of the alkyl substituents recited herein.
As used herein and unless otherwise indicated, the term “heteroaryl” as used herein alone or as part of another group refers to a 5- to 7-membered aromatic ring which includes 1, 2, 3 or 4 hetero atoms such as nitrogen, oxygen or sulfur and such rings fused to an aryl, cycloalkyl, heteroaryl or heterocycloalkyl ring (e g. benzothiophenyl, indolyl), and includes possible N-oxides. “Substituted heteroaryl” includes a heteroaryl group optionally substituted with 1 to 4 substituents, such as the substituents included above in the definition of “substituted alkyl” and “substituted cycloalkyl.” Substituted heteroaryl also includes fused heteroaryl groups which include, for example, quinoline, isoquinoline, indole, isoindole, carbazole, acridine, benzimidazole, benzofuran, isobenzofuran, benzothiophene, phenanthroline, purine, and the like.
Hereinafter, a structure and Preparation Example of an organometallic compound according to the present disclosure and an organic light-emitting diode including the same will be described.
Conventionally, an organometallic compound has been used as a dopant in a light-emitting layer of an organic light-emitting diode. For example, 2-phenylpyridine, and 2-phenylquinoline in which a fused ring is introduced to a pyridine moiety in a structure of 2-phenylpyridine are known as a main ligand structure of the organometallic compound. However, the conventional light-emitting dopant has a limit in improving efficiency and lifetime of the organic light-emitting diode. Thus, it is necessary to develop a new light-emitting dopant material. Accordingly, the inventors of the present disclosure have derived a light-emitting dopant material that can further improve the efficiency and lifespan of the organic light-emitting diode and thus have completed the present disclosure.
Specifically, an organometallic compound according to one implementation of the present disclosure may be represented by following Chemical Formula 1. In LA as a main ligand of Chemical Formula 1, a fused ring structure of thiophene having a sulfur (S) atom is introduced to a ring to which carbon (C) is connected among two rings connected to Ir (iridium) as a central coordination metal. Further, the organometallic compound may be represented by one selected from following Chemical Formula 2-1 to Chemical Formula 2-6, based on a connection position and an orientation of the thiophene fused ring. The inventors of the present disclose have experimentally identified that when the organometallic compound represented by Chemical Formula 1 was used as the dopant material of the phosphorescent light-emitting layer of the organic light-emitting diode, the light-emitting efficiency and the lifespan of the organic light-emitting diode were improved and the operation voltage thereof was lowered, and thus have completed the present disclosure:
Ir(LA)m(LB)n [Chemical Formula 1]
wherein in Chemical Formula 1,
LA may be represented by one selected from a group consisting of following Chemical Formula 2-1 to Chemical Formula 2-6,
LB may be a bidentate ligand represented by following Chemical Formula 3,
m may be 1, 2 or 3, n may be 0, 1 or 2, and a sum of m and n may be 3,
wherein in each of Chemical Formula 2-1 to Chemical Formula 2-6,
X may represent one selected from a group consisting of —CH2—, oxygen, —NH— and sulfur,
each of R1-1, R1-2, R1-3, R1-4, R2-1, R2-2, R3-1, R3-2, R4-1 and R4-2 may independently represent one selected from a group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof,
optionally, two adjacent functional groups among R1-1, R1-2, R1-3, R1-4, R2-1, R2-2, R3-1, R3-2, R4-1 and R4-2 may bind to each other to form a ring structure.
In the organometallic compound according to an implementation of the present disclosure, an ancillary ligand bound to the central coordination metal may be the bidentate ligand. The bidentate ligand may contain an electron donor, thereby increasing an amount of MLCT (metal to ligand charge transfer), thereby allowing the organic light-emitting diode to exhibit improved luminous properties such as high luminous efficiency and high external quantum efficiency.
A preferred auxiliary ligand according to the present disclosure may be a bidentate ligand represented by Chemical Formula 3. Chemical Formula 3 may be one selected from a group consisting of following Chemical Formula 4 and Chemical Formula 5:
wherein in Chemical Formula 4, each of R5-1, R5-2, R5-3, R5-4, R6-1, R6-2, R6-3 and R6-4 may independently represent one selected from a group consisting of hydrogen, deuterium, C1-C5 a straight-chain alkyl group, and a C1-C5 branched alkyl group, and optionally, two adjacent functional groups among R5-1, R5-2, R5-3, R5-4, R6-1, R6-2, R6-3 and R6-4 may bind to each other to form a ring structure,
wherein in Chemical Formula 5, each of R7, R8 and R9 may independently represent one selected from a group consisting of hydrogen, deuterium, a C1-C5 straight-chain alkyl group and a C1-C5 branched alkyl group, and optionally, two adjacent functional groups among R7, R8 and R9 may bind to each other to form a ring structure,
wherein the C1-C5 straight-chain alkyl group or the C1-C5 branched alkyl group may be substituted with at least one selected from a group consisting of deuterium and a halogen element.
The organometallic compound according to an implementation of the present disclosure may have a heteroleptic or homoleptic structure. For example, the organometallic compound according to an example embodiment of the present disclosure may have a heteroleptic structure in which in Chemical Formula 1, m is 1 and n is 2; or a heteroleptic structure in which in Chemical Formula 1, m is 2 and n is 1; or a homoleptic structure in which in Chemical Formula 1, m is 3 and n is 0.
A specific example of the compound represented by Chemical Formula 1 of the present disclosure may include one selected from a group consisting of following compounds 1 to 540. However, the specific example of the compound represented by Chemical Formula 1 of the present disclosure is not limited thereto as long as it meets the above definition of Chemical Formula 1:
According to one implementation of the present disclosure, the organometallic compound represented by Chemical Formula 1 of the present disclosure may be used as a dopant material achieving red phosphorescent or a green phosphorescence, preferably, as a dopant material achieving the green phosphorescence.
Referring to
Further, although not shown in
The first electrode 110 may act as a positive electrode, and may include ITO, IZO, tin-oxide, or zinc-oxide as a conductive material having a relatively large work function value. However, the present disclosure is not limited thereto.
The second electrode 120 may act as a negative electrode, and may include Al, Mg, Ca, or Ag as a conductive material having a relatively small work function value, or an alloy or combination thereof. However, the present disclosure is not limited thereto.
The hole injection layer 140 may be positioned between the first electrode 110 and the hole transport layer 150. The hole injection layer 140 may have a function of improving interface characteristics between the first electrode 110 and the hole transport layer 150, and may be selected from materials having appropriate conductivity. The hole injection layer 140 may include a compound selected from a group consisting of N1-phenyl-N4,N4-bis(4-(phenyl(tolyl)amino)phenyl)-N1-(tolyl)benzene-1,4-diamin (MTDATA), copper(II) phthalocyanine (CuPc), tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile (HATCN), 1,3,5-tris[4-(diphenylamino)phenyl]benzene (TDAPB), poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT/PSS), and N1,N1′-([1,1′-biphenyl]-4,4′-diyl)bis(N1,N4,N4)-triphenylbenzene-1,4-diamine). Preferably, the hole injection layer 140 may include N1,N1′-([1,1′-biphenyl]-4,4′-diyl)bis(N1,N4,N4-triphenylbenzene-1,4-diamine). However, the present disclosure is not limited thereto.
The hole transport layer 150 may be positioned adjacent to the light-emitting layer 160 and between the first electrode 110 and the light-emitting layer 160. A material of the hole transport layer 150 may include at least one compound selected from a group consisting of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD), N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB), 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP), N-(biphenyl-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)-9H-fluoren-2-amine, N-(biphenyl-4-yl)-N-(4-(9-phenyl-9H-carbazol-3-yl)phenyl)biphenyl)-4-amine, etc. Preferably, the material of the hole transport layer 150 may include NPB. However, the present disclosure is not limited thereto.
According to the present disclosure, the light-emitting layer 160 may be formed by doping a host material 160′ with the organometallic compound represented by Chemical Formula 1 as a dopant 160″ in order to improve luminous efficiency of the diode 100. The dopant 160″ may be used as a green or red light-emitting material, and preferably as a green phosphorescent material.
A doping concentration of the dopant 160″ according to example embodiment of the present disclosure may be adjusted to be within a range of 1 to 30% by weight based on a total weight of the host material 160′. However, the disclosure is not limited thereto. For example, the doping concentration may be in a range of 2 to 20 wt %, for example, 3 to 15 wt %, for example, 5 to 10 wt %, for example, 3 to 8 wt %, for example, 2 to 7 wt %, for example, 5 to 7 wt %, or for example, 5 to 6 wt %.
The light-emitting layer 160 according to example embodiment of the present disclosure contains the host material 160′ which is known in the art and may achieve an effect of the present disclosure while the layer 160 contains the organometallic compound represented by Chemical Formula 1 as the dopant 160″. For example, in accordance with the present disclosure, the host material 160′ may include a compound containing a carbazole group, and may preferably include one host material selected from a group consisting of CBP (carbazole biphenyl), mCP (1,3-bis(carbazol-9-yl), and the like. However, the disclosure is not limited thereto.
Further, the electron transport layer 170 and the electron injection layer 180 may be sequentially stacked between the light-emitting layer 160 and the second electrode 120. A material of the electron transport layer 170 requires high electron mobility such that electrons may be stably supplied to the light-emitting layer under smooth electron transport.
For example, the material of the electron transport layer 170 may be known to the art and may include at least one compound selected from a group consisting of Alq3 (tris(8-hydroxyquinolino)aluminum), 8-hydroxyquinolinolatolithium (Liq), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), 3-(4-biphenyl)4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), spiro-PBD, bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium (BAlq), bis(2-methyl 8-hydroxyquinoline) (triphenyl siloxy) aluminium (SAlq), 2,2′,2-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole (TPBi), oxadiazole, triazole, phenanthroline, benzoxazole, benzthiazole, and 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole. Preferably, the material of the electron transport layer 170 may include 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole. However, the present disclosure is not limited thereto.
The electron injection layer 180 serves to facilitate electron injection. A material of the electron injection layer may be known to the art and may include at least one compound selected from a group consisting of Alq3 (tris(8-hydroxyquinolino)aluminum), PBD), TAZ), spiro-PBD, BAlq, SAlq, etc. However, the present disclosure is not limited thereto. Alternatively, the electron injection layer 180 may be made of a metal compound. The metal compound may include, for example, one or more selected from a group consisting of Liq, LiF, NaF, KF, RbF, CsF, FrF, BeF2, MgF2, CaF2, SrF2, BaF2 and RaF2. However, the present disclosure is not limited thereto.
The organic light-emitting diode according to example embodiment of the present disclosure may be embodied as a white light-emitting diode having a tandem structure. The tandem organic light-emitting diode according to an illustrative embodiment of the present disclosure may be formed in a structure in which adjacent ones of two or more light-emitting stacks are connected to each other via a charge generation layer (CGL). The organic light-emitting diode may include at least two light-emitting stacks disposed on a substrate, wherein each of the at least two light-emitting stacks includes first and second electrodes facing each other, and the light-emitting layer disposed between the first and second electrodes to emit light in a specific wavelength band. The plurality of light-emitting stacks may emit light of the same color or different colors. In addition, one or more light-emitting layers may be included in one light-emitting stack, and the plurality of light-emitting layers may emit light of the same color or different colors.
In this case, the light-emitting layer included in at least one of the plurality of light-emitting stacks may contain the organometallic compound represented by Chemical Formula 1 according to the present disclosure as the dopants. Adjacent ones of the plurality of light-emitting stacks in the tandem structure may be connected to each other via the charge generation layer CGL including an N-type charge generation layer and a P-type charge generation layer.
As shown in
As shown in
Furthermore, an organic light-emitting diode according to an example embodiment of the present disclosure may include a tandem structure in which four or more light-emitting stacks and three or more charge generating layers are disposed between the first electrode and the second electrode.
The organic light-emitting diode according to example embodiment of the present disclosure may be used as a light-emitting element of each of an organic light-emitting display device and a lighting device. In one implementation,
As shown in
Although not shown explicitly in
The driving thin-film transistor Td is connected to the switching thin film transistor, and includes a semiconductor layer 3100, a gate electrode 3300, a source electrode 3520, and a drain electrode 3540.
The semiconductor layer 3100 may be formed on the substrate 3010 and may be made of an oxide semiconductor material or polycrystalline silicon. When the semiconductor layer 3100 is made of an oxide semiconductor material, a light-shielding pattern (not shown) may be formed under the semiconductor layer 3100. The light-shielding pattern prevents light from being incident into the semiconductor layer 3100 to prevent the semiconductor layer 3100 from being deteriorated due to the light. Alternatively, the semiconductor layer 3100 may be made of polycrystalline silicon. In this case, both edges of the semiconductor layer 3100 may be doped with impurities.
The gate insulating layer 3200 made of an insulating material is formed over an entirety of a surface of the substrate 3010 and on the semiconductor layer 3100. The gate insulating layer 3200 may be made of an inorganic insulating material such as silicon oxide or silicon nitride.
The gate electrode 3300 made of a conductive material such as a metal is formed on the gate insulating layer 3200 and corresponds to a center of the semiconductor layer 3100. The gate electrode 3300 is connected to the switching thin film transistor.
The interlayer insulating layer 3400 made of an insulating material is formed over the entirety of the surface of the substrate 3010 and on the gate electrode 3300. The interlayer insulating layer 3400 may be made of an inorganic insulating material such as silicon oxide or silicon nitride, or an organic insulating material such as benzocyclobutene or photo-acryl.
The interlayer insulating layer 3400 has first and second semiconductor layer contact holes 3420 and 3440 defined therein respectively exposing both opposing sides of the semiconductor layer 3100. The first and second semiconductor layer contact holes 3420 and 3440 are respectively positioned on both opposing sides of the gate electrode 3300 and are spaced apart from the gate electrode 3300.
The source electrode 3520 and the drain electrode 3540 made of a conductive material such as metal are formed on the interlayer insulating layer 3400. The source electrode 3520 and the drain electrode 3540 are positioned around the gate electrode 3300, and are spaced apart from each other, and respectively contact both opposing sides of the semiconductor layer 3100 via the first and second semiconductor layer contact holes 3420 and 3440, respectively. The source electrode 3520 is connected to a power line (not shown).
The semiconductor layer 3100, the gate electrode 3300, the source electrode 3520, and the drain electrode 3540 constitute the driving thin-film transistor Td. The driving thin-film transistor Td has a coplanar structure in which the gate electrode 3300, the source electrode 3520, and the drain electrode 3540 are positioned on top of the semiconductor layer 3100.
Alternatively, the driving thin-film transistor Td may have an inverted staggered structure in which the gate electrode is disposed under the semiconductor layer while the source electrode and the drain electrode are disposed above the semiconductor layer. In this case, the semiconductor layer may be made of amorphous silicon. In one example, the switching thin-film transistor (not shown) may have substantially the same structure as that of the driving thin-film transistor (Td).
In one example, the organic light-emitting display device 3000 may include a color filter 3600 absorbing the light generated from the electroluminescent element (light-emitting diode) 4000. For example, the color filter 3600 may absorb red (R), green (G), blue (B), and white (W) light. In this case, red, green, and blue color filter patterns that absorb light may be formed separately in different pixel areas. Each of these color filter patterns may be disposed to overlap each organic layer 4300 of the organic light-emitting diode 4000 to emit light of a wavelength band corresponding to each color filter. Adopting the color filter 3600 may allow the organic light-emitting display device 3000 to realize full-color.
For example, when the organic light-emitting display device 3000 is of a bottom emission type, the color filter 3600 absorbing light may be positioned on a portion of the interlayer insulating layer 3400 corresponding to the organic light-emitting diode 4000. In an optional embodiment, when the organic light-emitting display device 3000 is of a top emission type, the color filter may be positioned on top of the organic light-emitting diode 4000, that is, on top of a second electrode 4200. For example, the color filter 3600 may be formed to have a thickness of 2 to 5 μm.
In one example, a protective layer 3700 having a drain contact hole 3720 defined therein exposing the drain electrode 3540 of the driving thin-film transistor Td is formed to cover the driving thin-film transistor Td.
On the protective layer 3700, each first electrode 4100 connected to the drain electrode 3540 of the driving thin-film transistor Td via the drain contact hole 3720 is formed individually in each pixel area.
The first electrode 4100 may act as a positive electrode (anode), and may be made of a conductive material having a relatively large work function value. For example, the first electrode 4100 may be made of a transparent conductive material such as ITO, IZO or ZnO.
In one example, when the organic light-emitting display device 3000 is of a top-emission type, a reflective electrode or a reflective layer may be further formed under the first electrode 4100. For example, the reflective electrode or the reflective layer may include at least one of aluminum (Al), silver (Ag), nickel (Ni), or an aluminum-palladium-copper (APC) alloy.
A bank layer 3800 covering an edge of the first electrode 4100 is formed on the protective layer 3700. The bank layer 3800 exposes a center of the first electrode 4100 corresponding to the pixel area.
An organic layer 4300 is formed on the first electrode 4100. If necessary, the organic light-emitting diode 4000 may have a tandem structure. Regarding the tandem structure, reference may be made to
The second electrode 4200 is formed on the substrate 3010 on which the organic layer 4300 has been formed. The second electrode 4200 is disposed over the entirety of the surface of the display area and is made of a conductive material having a relatively small work function value and may be used as a negative electrode (a cathode). For example, the second electrode 4200 may be made of one of aluminum (Al), magnesium (Mg), and an aluminum-magnesium alloy (Al—Mg).
The first electrode 4100, the organic layer 4300, and the second electrode 4200 constitute the organic light-emitting diode 4000.
An encapsulation film 3900 is formed on the second electrode 4200 to prevent external moisture from penetrating into the organic light-emitting diode 4000. Although not shown explicitly in
Hereinafter, Preparation Example and Present Example of the present disclosure will be described. However, following Present Example is only one example of the present disclosure. The present disclosure is not limited thereto.
(1) Preparation of Ligand A
Step 1) Preparation of Ligand Compound A-2
Compound SM-1 (4.58 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound A-2 (4.72 g, 82%).
Step 2) Preparation of Ligand Compound A-1
Compound A-2 (5.76 g, 20 mmol), Compound SM-3 (4.28 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound A-1 (6.04 g, 80%).
Step 3) Preparation of Ligand Compound A
Compound A-1 (7.55 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound A (4.58 g, 64%).
(2) Preparation of Ligand Compound B
Step 1) Preparation of Ligand Compound B-2
Compound A-2 (5.76 g, 20 mmol), Compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound B-2 (6.50 g, 83%).
Step 2) Preparation of Ligand Compound B-1
Compound B-2 (7.83 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound B-1 (5.05 g, 68%).
Step 3) Preparation of Ligand Compound B
Compound B-1 (7.43 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere, and then a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound B (6.13 g, 82%).
(3) Preparation of Ligand Compound C
Step 1) Preparation of Ligand Compound C-2
Compound SM-5 (4.86 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound C-2 (4.77 g, 79%).
Step 2) Preparation of Ligand Compound C-1
Compound C-2 (6.04 g, 20 mmol), Compound SM-3 (4.28 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound C-1 (6.58 g, 84%).
Step 3) Preparation of Ligand Compound C
Compound C-1 (7.83 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound C (4.83 g, 65%).
(4) Preparation of Ligand Compound D
Step 1) Preparation of Ligand Compound D-2
Compound C-2 (6.04 g, 20 mmol), Compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain the Compound D-2 (6.81 g, 84%).
Step 2) Preparation of Ligand Compound D-1
Compound D-2 (8.11 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain the Compound D-1 (6.32 g, 82%).
Step 3) Preparation of Ligand Compound D
Compound D-1 (7.71 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere, and then a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound D (5.43 g, 70%).
(5) Preparation of Ligand Compound E
Step 1) Preparation of Ligand E-2
Compound SM-6 (4.58 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound E-2 (4.90 g, 85%).
Step 2) Preparation of Ligand Compound E-1
Compound E-2 (5.76 g, 20 mmol), Compound SM-3 (4.28 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound E-1 (6.42 g, 85%).
Step 3) Preparation of Ligand Compound E
Compound E-1 (7.55 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound E (4.86 g, 68%).
(6) Preparation of Ligand Compound F
Step 1) Preparation of Ligand Compound F-2
Compound E-2 (5.76 g, 20 mmol), Compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound F-2 (6.34 g, 81%).
Step 2) Preparation of Ligand Compound F-1
Compound F-2 (7.83 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound F-1 (6.17 g, 83%).
Step 3) Preparation of Ligand Compound F
Compound F-1 (7.43 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound F (5.01 g, 67%).
(7) Preparation of Ligand Compound G
Step 1) Preparation of Ligand Compound G-2
Compound SM-7 (4.86 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound G-2 (4.83 g, 80%).
Step 2) Preparation of Ligand Compound G-1
Compound G-2 (6.04 g, 20 mmol), Compound SM-3 (4.28 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound G-1 (6.58 g, 84%).
Step 3) Preparation of Ligand Compound G
Compound G-1 (7.83 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound G (4.76 g, 64%).
(8) Preparation of Ligand Compound H
Step 1) Preparation of Ligand Compound H-2
Compound G-2 (6.04 g, 20 mmol), Compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound H-2 (6.65 g, 82%).
Step 2) Preparation of Ligand Compound H-1
Compound H-2 (8.11 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound H-1 (6.25 g, 81%).
Step 3) Preparation of Ligand Compound H
Compound H-1 (7.71 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere, and then a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound H (5.19 g, 67%).
(9) Preparation of Ligand Compound I
Step 1) Preparation of Ligand Compound I-3
Compound SM-8 (4.58 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain the Compound I-3 (4.67 g, 81%).
Step 2) Preparation of Ligand Compound I-2
Compound I-3 (5.76 g, 20 mmol), Compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound I-2 (6.42 g, 82%).
Step 3) Preparation of Ligand Compound I-1
Compound I-2 (7.83 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound I-1 (5.80 g, 78%).
Step 4) Preparation of Ligand Compound I
Compound I-1 (7.43 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere and then a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound I (4.86 g, 65%).
(10) Preparation of Ligand Compound J
Step 1) Preparation of Ligand Compound J-3
Compound SM-9 (4.86 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound J-3 (4.71 g, 78%).
Step 2) Preparation of Ligand Compound J-2
Compound J-3 (6.04 g, 20 mmol), the compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain the Compound J-2 (6.49 g, 80%).
Step 3) Preparation of Ligand Compound J-1
Compound J-2 (8.11 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THE in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound J-1 (5.09 g, 66%).
Step 4) Preparation of Ligand Compound J
Compound J-1 (7.71 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere and then a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound J (6.36 g, 82%).
(11) Preparation of Ligand Compound K
Step 1) Preparation of Ligand Compound K-3
Compound SM-10 (4.58 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound K-3 (4.44 g, 77%).
Step 2) Preparation of Ligand Compound K-2
Compound K-3 (5.76 g, 20 mmol), Compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound K-2 (6.26 g, 80%).
Step 3) Preparation of Ligand Compound K-1
Compound K-2 (7.83 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THF in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound K-1 (6.17 g, 83%).
Step 4) Preparation of Ligand Compound K
Compound K-1 (7.43 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere, and then a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound K (5.08 g, 68%).
(12) Preparation of Ligand Compound L
Step 1) Preparation of Ligand Compound L-3
Compound SM-11 (4.86 g, 20 mmol), Compound SM-2 (3.67 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound L-3 (4.53 g, 75%).
Step 2) Preparation of Ligand Compound L-2
Compound L-3 (6.04 g, 20 mmol), Compound SM-4 (4.56 g, 20 mmol), Pd(PPh3)4 (2.31 g, 2 mmol), P(t-Bu)3 (0.81 g, 4 mmol) and NaOtBu (7.68 g, 80 mmol) were dissolved in 200 mL of toluene in a 250 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated under reflux and was stirred for 12 hours. After completion of a reaction, a temperature was lowered to room temperature, and an organic layer was extracted therefrom with dichloromethane and washed sufficiently with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and hexane to obtain Compound L-2 (6.33 g, 78%).
Step 3) Preparation of Ligand Compound L-1
Compound L-2 (8.11 g, 20 mmol) was dissolved in 80 mL of acetic acid and 25 mL of THE in a 250 mL round bottom flask under a nitrogen atmosphere, and then tert-butyl nitrite (5 mL, 38 mmol) was added to a mixed solution in a dropwise manner at 0° C. and the mixed solution was stirred. After completion of the stirring at 0° C. for 4 hours, a temperature was raised to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed with water sufficiently. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with dichloromethane and hexane to obtain Compound L-1 (5.01 g, 65%).
Step 4) Preparation of Ligand Compound L
Compound L-1 (7.71 g, 20 mmol) and sodium tert-butoxide (4 mL, 40 mmol) were added to 100 mL of DMSO-d6 in a 250 mL round bottom flask under a nitrogen atmosphere, and then a mixed solution was heated and stirred at 135° C. for 48 hours. After completion of a reaction, the reaction vessel was cooled to room temperature, and an organic layer was extracted therefrom with ethyl acetate, and washed thoroughly with water. Moisture was removed therefrom with anhydrous magnesium sulfate, and the solution was filtered using a filter and then was concentrated under reduced pressure and then was subjected to separation using column chromatography with ethyl acetate and dichloromethane to obtain Compound L (6.51 g, 84%).
(1) Preparation of Iridium Precursor Compound M′
Step 1) Preparation of Compound MM
A mixed solution in which Compound M (3.38 g, 20 mmol) and IrCl3 (2.39 g, 8.0 mmol) were dissolved in ethoxyethanol:distilled water=90 mL:30 mL was input into a 250 mL round bottom flask under a nitrogen atmosphere, and the mixed solution was stirred under reflux for 24 hours. After completion of a reaction, a temperature is lowered to room temperature, and a resulting solid is separated therefrom via filtration under reduced pressure. The solid was filtered using a filter and was sufficiently washed with water and cold methanol, and was subjected to filtration under reduced pressure repeatedly several times to obtain 4.24 g (94%) of the solid Compound MM.
Step 2) Preparation of Iridium Precursor Compound M′
In a 250 mL round bottom flask, Compound MM (4.51 g, 4 mmol) and silver trifluoromethanesulfonate (AgOTf, 3.02 g, 12 mmol) were dissolved in dichloromethane and a mixed solution was stirred at room temperature for 24 hours. After completion of a reaction, a solid precipitate is removed therefrom via filtration through celite. A resulting filtrate was filtered through a filter and was distilled under reduced pressure to obtain 5.34 g (90%) of the resulting solid Compound M′.
(2) Preparation of Iridium Precursor Compound B′
Step 1) Preparation of Compound BB
A mixed solution in which Compound B (7.47 g, 20 mmol) and IrCl3 (2.39 g, 8.0 mmol) were dissolved in ethoxyethanol:distilled water=90 mL:30 mL was input into a 250 mL round bottom flask under a nitrogen atmosphere and the mixed solution was heated under reflux and was stirred for 24 hours. After completion of a reaction, a temperature is lowered to room temperature, and a resulting solid is separated therefrom via filtration under reduced pressure. The solid was filtered using a filter and was sufficiently washed with water and cold methanol, and was subjected to filtration under reduced pressure repeatedly several times to obtain 7.00 g (90%) of the solid Compound BB.
Step 2) Preparation of Iridium Precursor Compound B′
In a 250 mL round bottom flask, Compound BB (7.78 g, 4 mmol) and silver trifluoromethanesulfonate (AgOTf, 3.02 g, 12 mmol) were dissolved in dichloromethane, and a mixed solution was stirred at room temperature for 24 hours. After completion of a reaction, a solid precipitate is removed therefrom via filtration through celite. A resulting filtrate was filtered through a filter and was distilled under reduced pressure to obtain 3.87 g (84%) of the resulting solid Compound B′.
(3) Preparation of Iridium Precursor Compound D′
Step 1) Preparation of Compound DD
A mixed solution in which Compound D (7.75 g, 20 mmol) and IrCl3 (2.39 g, 8.0 mmol) were dissolved in ethoxyethanol:distilled water=90 mL:30 mL was input into a 250 mL round bottom flask under a nitrogen atmosphere and the mixed solution was heated under reflux and was stirred for 24 hours. After completion of a reaction, a temperature is lowered to room temperature, and a resulting solid is separated therefrom via filtration under reduced pressure. The solid was filtered using a filter and was sufficiently washed with water and cold methanol, and was subjected to filtration under reduced pressure repeatedly several times to obtain 6.88 g (86%) of the solid Compound BB.
Step 2) Preparation of Iridium Precursor Compound D′
In a 250 mL round bottom flask, Compound DD (8.01 g, 4 mmol) and silver trifluoromethanesulfonate (AgOTf, 3.02 g, 12 mmol) were dissolved in dichloromethane and a mixed solution was stirred at room temperature for 24 hours. After completion of a reaction, a solid precipitate is removed therefrom via filtration through celite. A resulting filtrate was filtered through a filter and was distilled under reduced pressure to obtain 4.01 g (85%) of the resulting solid Compound D′.
(4) Preparation of Iridium Precursor Compound F′
Step 1) Preparation of Compound FF
A mixed solution in which Compound F (7.47 g, 20 mmol) and IrCl3 (2.39 g, 8.0 mmol) were dissolved in ethoxyethanol:distilled water=90 mL:30 mL was added to a 250 mL round bottom flask under a nitrogen atmosphere and the mixed solution was heated under reflux and was stirred for 24 hours. After completion of a reaction, a temperature is lowered to room temperature, and a resulting solid is separated therefrom via filtration under reduced pressure. The solid was filtered using a filter and was sufficiently washed with water and cold methanol, and was subjected to filtration under reduced pressure repeatedly several times to obtain 6.54 g (84%) of the solid Compound FF.
Step 2) Preparation of Iridium Precursor Compound F′
In a 250 mL round bottom flask, Compound FF (7.78 g, 4 mmol) and silver trifluoromethanesulfonate (AgOTf, 3.02 g, 12 mmol) were dissolved in dichloromethane and a mixed solution was stirred at room temperature for 24 hours. After completion of a reaction, a solid precipitate is removed therefrom via filtration through celite. A resulting filtrate was filtered through a filter and was distilled under reduced pressure to obtain 4.05 g (88%) of the resulting solid Compound F′.
1. Preparation of Iridium Compound 66
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand A (1.07 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 66 (1.00 g, 75%).
2. Preparation of Iridium Compound 67
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand B (1.12 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 67 (0.96 g, 71%).
3. Preparation of Iridium Compound 96
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand C (1.11 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 96 (1.03 g, 76%).
4. Preparation of Iridium Compound 97
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand D (1.16 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 97 (1.11 g, 81%).
5. Preparation of Iridium Compound 216
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand E (1.07 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 216 (1.14 g, 86%).
6. Preparation of Iridium Compound 217
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand F (1.12 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 217 (1.09 g, 81%).
7. Preparation of Iridium Compound 246
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand G (1.11 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 246 (1.07 g, 79%).
8. Preparation of Iridium Compound 247
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand H (1.16 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 247 (1.10 g, 80%).
9. Preparation of Iridium Compound 309
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand I (1.12 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 309 (0.96 g, 71%).
10. Preparation of Iridium Compound 319
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand J (1.16 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 319 (1.04 g, 76%).
11. Preparation of Iridium Compound 349
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand K (1.12 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 349 (1.19 g, 88%).
12. Preparation of Iridium Compound 359
We input the iridium precursor M′ (1.11 g, 1.5 mmol) and the ligand L (1.16 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=25:75 to obtain the iridium compound 359 (1.15 g, 84%).
13. Preparation of Iridium Compound 469
We input the iridium precursor B′ (1.72 g, 1.5 mmol) and the ligand N (0.47 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=50:50 to obtain the iridium compound 469 (1.23 g, 75%).
14. Preparation of Iridium Compound 470
We input the iridium precursor D′ (1.76 g, 1.5 mmol) and the ligand N (0.47 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=50:50 to obtain the iridium compound 470 (1.21 g, 72%).
15. Preparation of Iridium Compound 479
We input the iridium precursor F′ (1.72 g, 1.5 mmol) and the ligand N (0.47 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=50:50 to obtain the iridium compound 479 (1.28 g, 78%).
16. Preparation of Iridium Compound 509
We input the iridium precursor B′ (1.72 g, 1.5 mmol) and the ligand O (0.73 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=40:60 to obtain the iridium compound 509 (1.38 g, 80%).
17. Preparation of Iridium Compound 510
We input the iridium precursor D′ (1.76 g, 1.5 mmol) and the ligand O (0.73 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=40:60 to obtain the iridium compound 510 (1.39 g, 79%).
18. Preparation of Iridium Compound 519
We input the iridium precursor F′ (1.72 g, 1.5 mmol) and the ligand O (0.73 g, 3 mmol) into 2-ethoxyethanol (50 mL) and DMF (50 mL) in a 150 mL round bottom flask under a nitrogen atmosphere, and, thereafter, a mixed solution was heated and stirred at 130° C. for 24 hours. When a reaction was completed, a temperature was lowered to room temperature, and an organic layer was extracted therefrom using dichloromethane and distilled water, and moisture was removed therefrom by adding anhydrous magnesium sulfate thereto. A filtrate was obtained through filtration thereof and was depressurized to obtain a resulting crude product. The resulting crude product was purified using column chromatography under a condition of ethylacetate:hexane=40:60 to obtain the iridium compound 519 (1.40 g, 81%).
A glass substrate having a thin film of ITO (indium tin oxide) having a thickness of 1,000 Å coated thereon was washed, followed by ultrasonic cleaning with acetone. Then, the glass substrate was dried. Thus, an ITO transparent electrode was formed. HI-1 as a hole injection material was deposited on the ITO transparent electrode in a thermal vacuum deposition manner. Thus, a hole injection layer having a thickness of 60 nm was formed. then, NPB as a hole transport material was deposited on the hole injection layer in a thermal vacuum deposition manner. Thus, a hole transport layer having a thickness of 80 nm was formed. Then, CBP as a host material of a light-emitting layer was deposited on the hole transport layer in a thermal vacuum deposition manner. The Compound 66 as a dopant was doped into the host material at a doping concentration of 5%. Thus, the light-emitting layer of a thickness of 30 nm was formed. ET-1:Liq (1:1) (30 nm) as a material for an electron transport layer and an electron injection layer was deposited on the light-emitting layer. Then, 100 nm thick aluminum was deposited thereon to form a negative electrode. In this way, an organic light-emitting diode emitting green light was manufactured.
The HI-1 means N1,N1′-([1,1′-biphenyl]-4,4′-diyl)bis(N1,N4,N4-triphenylbenzene-1,4-diamine).
The ET-1 means 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole.
Organic light-emitting diodes of Present Examples 2 to 18 and Comparative Examples 1 to 7 were manufactured in the same manner as in Present Example 1, except that Compounds indicated in following Tables 1 to 2 were used instead of the Compound 66 as the dopant in the Present Example 1.
<Performance Evaluation of Organic Light-Emitting Diodes>
Regarding the organic light emitting diodes prepared according to Present Examples 1 to 18 and Comparative Examples 1 to 7, operation voltages and efficiency characteristics at 10 mA/cm2 current, and lifetime characteristics when being accelerated at 20 mA/cm2 were measured. Thus, operation voltage (V), EQE (External Quantum Efficiency) (%), and LT95 (%) were measured and were converted to values relative to values of Comparative Example 1, and results are shown in Tables 1 to 2 below. LT95 refers to a lifetime evaluation scheme and means a time it takes for an organic light-emitting diode to lose 5% of initial brightness thereof.
Structures of Ref-1 to Ref-7 as dopant materials in Comparative Examples 1 to 7 in the above Table 1 are as follows.
It may be identified from the results of the above Table 1 to Table 2 that in the organic light-emitting diode in which the organometallic compound of each of Present Examples 1 to 18 according to the present disclosure is used as the dopant of the light-emitting layer of the diode, the operation voltage of the diode is lowered, and the maximum luminous efficiency, the external quantum efficiency (EQE) and the lifetime (LT95) of the diode are improved, compared to those in Comparative Example 1.
A scope of protection of the present disclosure should be construed by the scope of the claims, and all technical ideas within the scope equivalent thereto should be construed as being included in the scope of the present disclosure. Although the example embodiments of the present disclosure have been described in more detail with reference to the accompanying drawings, the present disclosure is not necessarily limited to these embodiments. The present disclosure may be implemented in various modified manners within the scope not departing from the technical idea of the present disclosure. Accordingly, the example embodiments disclosed in the present disclosure are not intended to limit the technical idea of the present disclosure, but to describe the present disclosure. the scope of the technical idea of the present disclosure is not limited by the example embodiments. Therefore, it should be understood that the example embodiments as described above are illustrative and non-limiting in all respects. The scope of protection of the present disclosure should be interpreted by the claims, and all technical ideas within the scope of the present disclosure should be interpreted as being included in the scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0188298 | Dec 2021 | KR | national |
