Organometallic compound and organic light-emitting diode comprising the same

Abstract

A novel organometallic compound represented by the following chemical formula 1 is disclosed. The organometallic compound acts as a dopant for the light-emitting layer of an organic light-emitting diode (OLED). Consequently, the diode's operating voltage is reduced, and its luminous efficiency and lifespan are improved: #imgabs0#

Description

Technical Field

[0001] The present disclosure relates to an organometallic compound, and more particularly, to an organometallic compound having phosphorescent properties, and an organic light emitting diode and a display device including the same. Background Art

[0002] As display devices are applied to various fields, interest in display devices is increasing. One of these display devices is an organic light emitting display device including an organic light emitting diode (OLED), which is being rapidly developed.

[0003] In an organic light-emitting diode (OLED), when charges are injected into the light-emitting layer formed between the positive and negative electrodes, electrons and holes recombine in the light-emitting layer to form excitons, and the energy of the excitons is converted into light. Consequently, OLEDs emit light. Compared to conventional display devices, OLEDs can operate at low voltages, consume relatively little power, exhibit excellent color, and can be used in various ways. Flexible substrates can be applied to OLEDs to provide flexible or foldable devices. Furthermore, the size of OLEDs can be freely adjusted. Summary of the Invention

[0004] Compared to liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs) have superior viewing angles and contrast, and because OLEDs do not require a backlight, they are lightweight and ultra-thin. OLEDs can include multiple organic layers between a negative electrode (e.g., an electron injection electrode, cathode, etc.) and a positive electrode (e.g., a hole injection electrode, anode, etc.). The multiple organic layers can include a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron blocking layer, a light-emitting layer, an electron transport layer, etc.

[0005] In this organic light-emitting diode structure, when voltage is applied to the two electrodes, electrons and holes are injected into the light-emitting layer from the cathode and anode, respectively, and thus excitons are generated in the light-emitting layer, which then drop to the ground state to emit light.

[0006] The organic materials used in organic light-emitting diodes can be broadly divided into luminescent materials and charge transport materials. The luminescent material is a key factor in determining the luminous efficiency of organic light-emitting diodes. The luminescent material must have high quantum efficiency, excellent electron and hole mobility, and must be uniformly and stably present in the luminescent layer. Luminescent materials can be categorized by light color, emitting blue, red, or green light. Chromogenic materials can include a host and a dopant to enhance color purity and luminous efficiency through energy transfer.

[0007] In recent years, there has been a trend toward using phosphorescent materials instead of fluorescent materials for light-emitting layers. When fluorescent materials are used, singlet states, which represent approximately 25% of the excitons generated in the light-emitting layer, contribute to light emission, while triplets, which represent the majority of the 75% of excitons generated in the light-emitting layer, are dissipated as heat. However, when phosphorescent materials are used, both singlet and triplet states contribute to light emission.

[0008] Conventionally, organometallic compounds are used as phosphorescent materials used in organic light-emitting diodes. Research and development of phosphorescent materials are constantly needed to solve the problems of low efficiency and lifespan.

[0009] Therefore, an object of the present invention is to provide an organic metal compound capable of reducing operating voltage and improving efficiency and lifespan, and an organic light emitting diode including an organic light emitting layer containing the same.

[0010] The purpose of the present disclosure is not limited to the above-mentioned purpose. Other unmentioned purposes and advantages of the present disclosure can be understood from the following description and can be more clearly understood from the embodiments of the present disclosure. In addition, it is easy to understand that the purposes and advantages of the present disclosure can be achieved using the means shown in the claims and their combinations.

[0011] To achieve the above object, the present disclosure provides an organometallic compound having a novel structure represented by the following Chemical Formula 1, and an organic light emitting diode in which a light emitting layer includes the same as a dopant of the light emitting layer.

[0012]

[0013] Wherein in the chemical formula 1, M may represent one selected from the group consisting of Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt and Au;

[0014] R may represent a cyclic structure fused to a pair selected from a pair of X5 and X6, a pair of X6 and X7, and a pair of X7 and X8;

[0015] X1 to X4 can be independently selected from one of CR5 and N;

[0016] Alternatively, two R5 on two adjacent ones of X1 to X4 may be linked to each other to form a cyclic structure comprising one selected from the group consisting of a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C2-C20 heteroaralkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group;

[0017] Y may represent one selected from the group consisting of BR6, CR6R7, C=O, CNR6, SiR6R7, NR6, PR6, AsR6, SbR6, P(O)R6, P(S)R6, P(Se)R6, As(O)R6, As(S)R6, As(Se)R6, Sb(O)R6, Sb(S)R6, Sb(Se)R6, O, S, Se, Te, SO, SO2, SeO, SeO2, TeO and TeO2;

[0018] X5 to X8 may each independently represent CR8;

[0019] R5 to R8 may each independently represent one selected from the group consisting of hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkenyl, substituted or unsubstituted C2-C20 heteroalkenyl, alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, alkoxy, amino, silyl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, and phosphino;

[0020] (Z1-Z2) may represent a bidentate ligand; and

[0021] M may be 1, 2 or 3, n may be 0, 1 or 2, and the sum of m and n may be the oxidation number of the metal M.

[0022] The organometallic compound according to the present disclosure may be used as a dopant of a light-emitting layer of an organic light-emitting diode, thereby reducing the operating voltage of the organic light-emitting diode and improving the efficiency and lifespan characteristics of the organic light-emitting diode.

[0023] The effects of the present disclosure are not limited to the above-mentioned effects, and other unmentioned effects will be clearly understood by those skilled in the art from the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The present disclosure will become more fully understood from the following detailed description and the accompanying drawings, which are given by way of illustration only and thus are not limiting of the present disclosure.

[0025] Figure 1 is a cross-sectional view schematically illustrating an organic light emitting diode in which a light emitting layer includes an organometallic compound according to an illustrative embodiment of the present disclosure.

[0026] Figure 2is a cross-sectional view schematically illustrating an organic light emitting diode having a tandem structure including two light emitting stacks and including the organometallic compound represented by Chemical Formula 1 according to an illustrative embodiment of the present disclosure.

[0027] Figure 3 is a cross-sectional view schematically illustrating an organic light emitting diode having a tandem structure including three light emitting stacks and including the organometallic compound represented by Chemical Formula 1 according to an illustrative embodiment of the present disclosure.

[0028] Figure 4 is a cross-sectional view schematically illustrating an organic light emitting display device including an organic light emitting diode according to an illustrative embodiment of the present disclosure. DETAILED DESCRIPTION

[0029] The advantages and features of the present disclosure, as well as the methods for achieving these advantages and features, will be described in detail below and in the accompanying drawings. Figure 1 The following detailed description of the embodiments will become apparent. However, the content of the present disclosure is not limited to the embodiments disclosed below, but can be implemented in a variety of different forms. Therefore, these embodiments are only provided to make the present disclosure complete and to fully inform those of ordinary skill in the art to which the present disclosure belongs of the scope of the present disclosure, and the scope of the present disclosure is limited only by the scope of the claims.

[0030] The shapes, sizes, proportions, angles, numbers, etc. disclosed in the accompanying drawings for describing the embodiments of the present disclosure are illustrative, and the present disclosure is not limited thereto. The same reference numerals refer to the same elements here. In addition, in order to simplify the description, descriptions and details of well-known steps and elements are omitted. In addition, in the following detailed description of the present disclosure, many specific details are set forth to provide a comprehensive understanding of the present disclosure. However, it is understood that the invention can be implemented without these specific details. In other cases, well-known methods, procedures, elements and circuits are not described in detail so as not to unnecessarily obscure various aspects of the present disclosure.

[0031] The terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the present disclosure. As used herein, the singular constructions "a" and "an" are intended to also include plural constructions, unless the context clearly indicates otherwise. It should be further understood that the terms "comprise," "including," "contain," and "comprising" used in this specification refer to the presence of the described features, integers, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, operations, elements, components, and / or parts thereof. As used herein, the term "and / or" includes any and all combinations of one or more related listed items. For example, an expression such as "at least one," when placed in front of a list of elements, can modify the entire list of elements without modifying a single element in the list. When interpreting numerical values, errors or tolerances may occur even without a clear description.

[0032] Furthermore, it is to 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 directly disposed on the second element, or may be indirectly disposed on the second element, with a third element or layer disposed between the first and second elements or layers. It is to 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. It is to 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 be present.

[0033] Further, as used herein, when a layer, film, region, plate, etc. is set on the "up" or "top" of another layer, film, region, plate, etc., the former can directly contact the latter or still another layer, film, region, plate, etc. can be set between the former and the latter. As used herein, when a layer, film, region, plate, etc. is directly set on the "up" or "top" of another layer, film, region, plate, etc., the former directly contacts the latter, and another layer, film, region, plate, etc. is not set between the former and the latter. In addition, as used herein, when a layer, film, region, plate, etc. is set on the "bottom" or "below" of another layer, film, region, plate, etc., the former can directly contact the latter, or another layer, film, region, plate, etc. can be set between the former and the latter. As used herein, when a layer, film, region, plate, etc. is directly set on the "bottom" or "below" of another layer, film, region, plate, etc., the former directly contacts the latter, and another layer, film, region, plate, etc. is not set between the former and the latter.

[0034] In descriptions of temporal relationships, such as a temporal precedence relationship between two events, such as "after," "subsequently," "before," etc., unless "directly after," "directly subsequent," or "directly before" is not specified, another event may occur in between.

[0035] It will be understood that although the terms "first," "second," "third," etc. may be used herein to describe various elements, components, regions, layers, and / or portions, these elements, components, regions, layers, and / or portions should not be limited by these terms. These terms are used to distinguish one element, component, region, layer, or portion from another element, component, region, layer, or portion. Thus, a first element, component, region, layer, or portion described below could be referred to as a second element, component, region, layer, or portion without departing from the spirit and scope of the present disclosure.

[0036] The features of the various embodiments of the present disclosure may be partially or completely combined with each other, and may be technically related to or interoperable with each other. The various embodiments may be implemented independently of each other, or may be implemented together in an associated relationship.

[0037] When interpreting a numerical value, the numerical value is interpreted as including a range of error unless otherwise expressly stated.

[0038] 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 can be directly on, connected to or coupled to the other element or layer, or one or more intervening elements or layers may be present. Additionally, it will be understood that when an element or layer is referred to as being “between” two elements or layers, it can be the only element or layer between the two elements or layers, or one or more intervening elements or layers may also be present.

[0039] The features of the various embodiments of the present disclosure may be partially or completely combined with each other, and may be technically related or interoperable with each other. The various embodiments may be implemented independently of each other, or may be implemented together in an associated relationship.

[0040] Unless otherwise defined, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the concepts of the present disclosure belong. It will be further understood that the terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning consistent with their meaning in the relevant technical context and will not be interpreted in an idealized or overly formal sense unless so explicitly defined in the present disclosure.

[0041] As used herein, the phrase "adjacent substituents are linked to form a ring (or cyclic structure)" means that adjacent substituents can be linked to form a substituted or unsubstituted alicyclic or aromatic ring. The phrase "adjacent substituents" of a substituent can refer to a substituent that replaces an atom directly connected to the atom substituted by the substituent, a substituent that is spatially closest to the substituent, or a substituent that replaces the atom substituted by the substituent. For example, two substituents that replace ortho positions in a benzene ring structure and two substituents that replace the same carbon in an alicyclic ring can be interpreted as "adjacent substituents."

[0042] The structure of the organometallic compound according to the present disclosure and an organic light emitting diode including the same will be described below.

[0043] Conventionally, organometallic compounds have been used as dopants in the light-emitting layers of organic light-emitting diodes (OLEDs). For example, 2-phenylpyridine and 2-phenylquinoline, a pyridine moiety with a fused ring, are known primary ligand structures of organometallic compounds. However, conventional luminescent dopants have limitations in improving the efficiency and lifespan of OLEDs. Therefore, there is a need to develop new luminescent dopant materials. Therefore, the inventors of the present disclosure have derived a luminescent dopant material that can further improve the efficiency and lifespan of OLEDs, leading to the completion of the present disclosure.

[0044] Specifically, the organometallic compound according to one embodiment of the present disclosure may be represented by the following Chemical Formula 1. In the main ligand of the following Chemical Formula 1, a fused ring of an "R" structure is introduced into the ring to which carbon (C) is connected in the two rings connected to the central coordination metal M. Therefore, in the organometallic compound of the present disclosure, [five-membered ring]-[five-membered ring]-[six-membered ring] is sequentially fused with [six-membered ring] to which carbon (C) is connected in the two rings connected to the central coordination metal M. When the organometallic compound represented by the following Chemical Formula 1 is used as a dopant material for the light-emitting layer of an organic light-emitting diode, the luminous efficiency and life of the organic light-emitting diode can be improved, and its operating voltage can be reduced:

[0045]

[0046] Wherein in the chemical formula 1, M may represent one selected from the group consisting of Mo, W, Re, Ru, Os, Rh, Ir, Pd, Pt and Au;

[0047] R may represent a cyclic structure fused to a pair selected from a pair of X5 and X6, a pair of X6 and X7, and a pair of X7 and X8;

[0048] X1 to X4 can be independently selected from one of CR5 and N;

[0049] Alternatively, two R5 on two adjacent ones of X1 to X4 are connected to each other to form a cyclic structure, wherein the cyclic structure includes one selected from the group consisting of a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C2-C20 heteroaralkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group;

[0050] Y may represent one selected from the group consisting of BR6, CR6R7, C=O, CNR6, SiR6R7, NR6, PR6, AsR6, SbR6, P(O)R6, P(S)R6, P(Se)R6, As(O)R6, As(S)R6, As(Se)R6, Sb(O)R6, Sb(S)R6, Sb(Se)R6, O, S, Se, Te, SO, SO2, SeO, SeO2, TeO and TeO2;

[0051] X5 to X8 may each independently represent CR8;

[0052] R5 to R8 may each independently represent one selected from the group consisting of hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkenyl, substituted or unsubstituted C2-C20 heteroalkenyl, alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, alkoxy, amino, silyl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, and phosphino;

[0053] (Z1-Z2) may represent a bidentate ligand; and

[0054] M may be 1, 2 or 3, n may be 0, 1 or 2, and the sum of m and n may be the oxidation number of the metal M.

[0055] The structure of Chemical Formula 1 as the organometallic compound according to the present disclosure is characterized in that, in the main ligand, a fused ring of "R" is introduced into the ring to which carbon (C) is connected among the two rings connected to the central coordinated metal M. Further, the substructures of the organometallic compound can be classified based on the structure of the ring to which nitrogen (N) is connected among the two rings connected to the central coordinated metal M.

[0056] Specifically, the substructures of Chemical Formula 1 of the present disclosure may include a first substructure in which a six-membered ring is fused to a ring connected to nitrogen (N), and a second substructure in which a six-membered ring and a five-membered ring are fused thereto. The first substructure may include "Chemical Formulas 2 to 5," and the second substructure may include "Chemical Formulas 6 to 11."

[0057] According to one embodiment of the present disclosure, the Chemical Formula 1 may be one selected from the group consisting of the following Chemical Formulas 2 to 5:

[0058]

[0059]

[0060] In each of the Chemical Formulas 2 to 5,

[0061] X9 to X 16 Each independently represents one selected from CR9 and N;

[0062] Or, X9 to X 16 Two adjacent R9 in the R group may be connected to each other to form a cyclic structure, wherein the cyclic structure includes one selected from the group consisting of a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C2-C20 heteroaralkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group;

[0063] R9 may represent one selected from the group consisting of hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkenyl, substituted or unsubstituted C2-C20 heteroalkenyl, alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, alkoxy, amino, silyl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, and phosphino;

[0064] M, Y, X1 to X8, R, R1 to R8, (Z1-Z2), m and n may be the same as defined above or in the claims.

[0065] According to another implementation of the present disclosure, the chemical formula 1 may be selected from the following chemical formulas:

[0066] One of the group consisting of Formula 6 to Chemical Formula 11:

[0067]

[0068]

[0069]

[0070] In each of the Chemical Formulas 6 to 11,

[0071] X 17 To X 20 Can each independently represent a member selected from CR 10 and one of N;

[0072] Or, X 17 To X 20 The two adjacent R 10 may be connected to each other to form a cyclic structure comprising one selected from the group consisting of a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 heterocycloalkyl group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C2-C20 heteroaralkyl group, a substituted or unsubstituted C3-C20 cycloalkenyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group;

[0073] Y1 may represent a selection from CR 11 R 12 NR 11 One of the group consisting of , O and S;

[0074] R 10 to R 12 each independently represents one selected from the group consisting of hydrogen, deuterium, halogen, hydroxyl, cyano, nitro, amidino, hydrazine, hydrazone, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C3-C20 cycloalkenyl, substituted or unsubstituted C2-C20 heteroalkenyl, alkynyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, alkoxy, amino, silyl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, and phosphino;

[0075] M, Y, X1 to X8, R, R1 to R8, (Z1-Z2), m and n may be the same as defined above or in the claims.

[0076] When a metal complex having a large atomic number of iridium (Ir) or platinum (Pt) is used, phosphorescence can be effectively obtained even at room temperature. Therefore, in the organometallic compound according to an embodiment of the present disclosure, the central coordination metal (M) is preferably one of iridium (Ir) or platinum (Pt), for example, more preferably iridium (Ir). However, the present disclosure is not limited thereto.

[0077] In the organometallic compound according to an embodiment of the present disclosure, the auxiliary ligand bound to the central coordinating metal may be a bidentate ligand. The bidentate ligand may contain an electron donor, thereby increasing the amount of MLCT (metal-to-ligand charge transfer), thereby enabling the organic light-emitting diode to exhibit improved luminescence characteristics, such as high luminous efficiency and high external quantum efficiency.

[0078] The organometallic compound according to the embodiment of the present disclosure may have a heteroleptic structure or a homoleptic structure. For example, the organometallic compound according to the embodiment of the present disclosure may have a heteroleptic structure in which m is 1 and n is 2 in Chemical Formula 1; or a heteroleptic structure in which m is 2 and n is 1; or a homoleptic structure in which m is 3 and n is 0.

[0079] Specific examples of the compound represented by Chemical Formula 1 of the present disclosure may include one selected from the group consisting of the following compounds 1 to 884. However, as long as the definition of the above Chemical Formula 1 is met, the specific examples of the compound represented by Chemical Formula 1 of the present disclosure are not limited thereto:

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] According to one embodiment of the present disclosure, the organometallic compound represented by Chemical Formula 1 of the present disclosure may be used as a dopant material for realizing red phosphorescence or green phosphorescence, preferably, as a dopant material for realizing red phosphorescence.

[0136] Reference Figure 1According to an embodiment of the present disclosure, an organic light emitting diode 100 may be provided, which includes a first electrode 110; a second electrode 120 facing the first electrode 110; and an organic layer 130 disposed between the first electrode 110 and the second electrode 120. The organic layer 130 may include a light emitting layer 160, and the light emitting layer 160 may include a host material 160' and a dopant 160". The dopant 160" may be made of an organic metal compound represented by Chemical Formula 1. In addition, in the organic light emitting diode 100, the organic layer 130 disposed between the first electrode 110 and the second electrode 120 may be formed by sequentially stacking a hole injection layer 140 (HIL), a hole transport layer 150 (HTL), a light emitting layer 160 (EML), an electron transport layer 170 (ETL), and an electron injection layer 180 (EIL) on the first electrode 110. The second electrode 120 may be formed on the electron injection layer 180, and a protective layer may be formed thereon.

[0137] Further, although Figure 1 Although not explicitly shown, a hole transport auxiliary layer may be further added between the hole transport layer 150 and the light-emitting layer 160. The hole transport auxiliary layer may contain a compound with excellent hole transport properties and may reduce the difference between the HOMO energy levels of the hole transport layer 150 and the light-emitting layer 160, thereby adjusting the hole injection characteristics. Consequently, hole accumulation at the interface between the hole transport auxiliary layer and the light-emitting layer 160 may be reduced, thereby reducing the quenching phenomenon in which excitons disappear at the interface due to polarons. Consequently, device degradation may be reduced, and the device may be stabilized, thereby improving its efficiency and lifespan.

[0138] The first electrode 110 may serve as a positive electrode and may be made of ITO, IZO, tin oxide, or zinc oxide, which are conductive materials having a relatively large work function value. However, the present disclosure is not limited thereto.

[0139] The second electrode 120 may serve as a negative electrode and may include Al, Mg, Ca, or Ag, which is a conductive material having a relatively small work function value, or an alloy or combination thereof. However, the present disclosure is not limited thereto.

[0140] The hole injection layer 140 may be located between the first electrode 110 and the hole transport layer 150. The hole injection layer 140 may have a function of improving the interface characteristics between the first electrode 110 and the hole transport layer 150, and may be selected from a material having appropriate conductivity. The hole injection layer 140 may include one or more compounds selected from the group consisting of MTDATA, CuPc, TCTA, HATCN, TDAPB, 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.

[0141] The hole transport layer 150 may be adjacent to the light emitting layer and located between the first electrode 110 and the light emitting layer 160. The material of the hole transport layer 150 may include a compound selected from the group consisting of TPD, NPB, 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.

[0142] According to the present disclosure, in order to improve the luminous efficiency of the diode 100, the light-emitting layer 160 can be formed by doping the host material 160' with the organic metal compound represented by Chemical Formula 1 as a dopant 160". The dopant 160" can serve as a green or red light-emitting material, preferably as a red phosphorescent material.

[0143] The doping concentration of the dopant 160 ″ according to the present disclosure may be adjusted to be in the range of 1 to 30 wt % based on the total weight of the host material 160 ′. However, the present disclosure is not limited thereto. For example, the doping concentration may be in the 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 6 wt %, for example, 2 to 5 wt %, or for example, 2 to 3 wt %.

[0144] The light-emitting layer 160 according to the present disclosure includes a host material 160' known in the art that can achieve the effects of the present disclosure, and the layer 160 includes an organic metal compound represented by Chemical Formula 1 as a dopant 160". For example, according to the present disclosure, the host material 160' may include a compound containing a carbazole group, and may preferably include a host material selected from the group consisting of CBP (carbazole biphenyl), mCP (1,3-bis (carbazole-9-yl), etc. However, the present disclosure is not limited thereto.

[0145] Furthermore, 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. The material of the electron transport layer 170 needs to have high electron mobility so that electrons can be stably supplied to the light emitting layer under smooth electron transport.

[0146] For example, the material of the electron transport layer 170 may include a compound selected from the group consisting of: Alq3 (tris (8-hydroxyquinoline) aluminum), Liq (8-hydroxyquinoline lithium), PBD (2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxazole), TAZ (3- (4-biphenyl) 4-phenyl -5-tert-butylphenyl -1,2,4-triazole), spiro-PBD, BAlq (bis (2-methyl-8-hydroxyquinoline) -4- (phenylphenol) aluminum), SAlq, TPBi (2,2',2-(1,3,5-benzoyl)-tri(1-phenyl-1-H-benzimidazole), oxadiazole, triazole, phenanthroline, benzoxazole, benzothiazole, and 2-(4-(9,10-di(naphthalene-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(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole. However, the present disclosure is not limited thereto.

[0147] The electron injection layer 180 is used to promote electron injection, and the material of the electron injection layer may include a compound selected from the group consisting of Alq3 (tris (8-hydroxyquinoline) aluminum), PBD, TAZ, spiro-PBD, BAlq, SAlq, etc. However, the present disclosure is not limited thereto. In addition, the electron injection layer 180 may be made of a metal compound. For example, the metal compound may include one or more selected from the 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.

[0148] The organic light emitting diode according to the present disclosure may be embodied as a white light emitting diode having a tandem structure. The tandem organic light emitting diode according to the illustrative embodiment of the present disclosure may be formed into a structure in which two or more adjacent light emitting stacks are connected to each other through 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 a light emitting layer disposed between the first and second electrodes to emit light in a specific wavelength band.

[0149] In this case, the light-emitting layer included in at least one of the plurality of light-emitting stacks may include an organometallic compound represented by Chemical Formula 1 of the present disclosure as a dopant. Adjacent light-emitting stacks in the series structure may be connected to each other through a charge generation layer (CGL) including an N-type charge generation layer and a P-type charge generation layer.

[0150] Figure 2 and Figure 3 are cross-sectional views schematically illustrating an organic light emitting diode in a series structure having two light emitting stacks and an organic light emitting diode in a series structure having three light emitting stacks according to some embodiments of the present disclosure.

[0151] like Figure 2 As shown, the organic light emitting diode 100 according to the present disclosure includes a first electrode 110 and a second electrode 120 facing each other, and an organic layer 230 located between the first electrode 110 and the second electrode 120. The organic layer 230 may be located between the first electrode 110 and the second electrode 120, and may include a first light emitting stack ST1 including a first light emitting layer 261, a second light emitting stack ST2 disposed between the first light emitting stack ST1 and the second electrode 120 and including a second light emitting layer 262, and a charge generation layer CGL disposed between the first and second light emitting stacks ST1 and ST2. The charge generation layer CGL may include an N-type charge generation layer 291 and a P-type charge generation layer 292. At least one of the first light emitting layer 261 and the second light emitting layer 262 may contain an organic metal compound represented by Chemical Formula 1 according to the present disclosure as a dopant. For example, as Figure 2 As shown, the second light emitting layer 262 of the second light emitting stack ST2 may include a host material 262' and a dopant 262" made of an organic metal compound represented by Chemical Formula 1 doped therein.

[0152] like Figure 3As shown, the organic light emitting diode 100 according to the present disclosure includes a first electrode 110 and a second electrode 120 facing each other, and an organic layer 330 located between the first electrode 110 and the second electrode 120. The organic layer 330 may be located between the first electrode 110 and the second electrode 120, and may include a first light emitting stack ST1 including a first light emitting layer 261, a second light emitting stack ST2 including a second light emitting layer 262, a third light emitting stack ST3 including a third light emitting layer 263, a first charge generation layer CGL1 located between the first and second light emitting stacks ST1 and ST2, and a second charge generation layer CGL2 located between the second and third light emitting stacks ST2 and ST3. The first charge generation layer CGL1 may include an N-type charge generation layer 291 and a P-type charge generation layer 292. The second charge generation layer CGL2 may include an N-type charge generation layer 293 and a P-type charge generation layer 294. At least one of the first light emitting layer 261, the second light emitting layer 262, and the third light emitting layer 263 may contain the organic metal compound represented by Chemical Formula 1 according to the present disclosure as a dopant. For example, as Figure 3 As shown, the second light emitting layer 262 of the second light emitting stack ST2 may include a host material 262' and a dopant 262" made of an organic metal compound represented by Chemical Formula 1 doped therein.

[0153] Furthermore, the organic light emitting diode according to an embodiment of the present disclosure may include a tandem structure in which four or more light emitting stacks and three or more charge generation layers are disposed between a first electrode and a second electrode.

[0154] The organic light emitting diode according to the present disclosure can be used as a light emitting element in each of an organic light emitting display device and an illumination device. In an embodiment, Figure 4 is a cross-sectional view schematically illustrating an organic light emitting display device including an organic light emitting diode according to some embodiments of the present disclosure.

[0155] like Figure 4 As shown, the organic light emitting display device 3000 includes a substrate 3010, an organic light emitting diode 4000, and an encapsulation film 3900 covering the organic light emitting diode 4000. A driving thin film transistor Td as a driving element and the organic light emitting diode 4000 connected to the driving thin film transistor Td are located on the substrate 3010.

[0156] Despite Figure 1 Although not explicitly shown, gate lines and data lines intersecting each other to define pixel areas, power lines extending parallel to and spaced apart from one of the gate lines and data lines, switching thin film transistors connected to the gate lines and data lines, and storage capacitors connected to one electrode of the thin film transistor and the power line are further formed on the substrate 3010.

[0157] 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 .

[0158] 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 may be formed under the semiconductor layer 3100. The light shielding pattern may prevent light from entering the semiconductor layer 3100, thereby preventing the semiconductor layer 3100 from being degraded by 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.

[0159] A gate insulating layer 3200 made of an insulating material is formed on the entire 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.

[0160] A gate electrode 3300 made of a conductive material such as metal is formed on the gate insulating layer 3200 and corresponds to the center of the semiconductor layer 3100. The gate electrode 3300 is connected to the switching thin film transistor.

[0161] An interlayer insulating layer 3400 made of an insulating material is formed on the entire surface of the substrate 3010 and 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.

[0162] The interlayer insulating layer 3400 has first and second semiconductor layer contact holes 3420 and 3440 respectively exposing opposite sides of the semiconductor layer 3100 as defined herein. The first and second semiconductor layer contact holes 3420 and 3440 are respectively disposed on opposite sides of the gate 3300 and spaced apart from the gate 3300.

[0163] A source electrode 3520 and a 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 provided around the gate electrode 3300 and are spaced apart from each other, and contact two opposite sides of the semiconductor layer 3100 through the first and second semiconductor layer contact holes 3420 and 3440, respectively. The source electrode 3520 is connected to a power supply line.

[0164] The semiconductor layer 3100 , the gate electrode 3300 , the source electrode 3520 , and the drain electrode 3540 constitute a driving thin film transistor Td. The driving thin film transistor Td has a coplanar structure, wherein the gate electrode 3300 , the source electrode 3520 , and the drain electrode 3540 are disposed on top of the semiconductor layer 3100 .

[0165] Alternatively, the driving thin film transistor Td may have an inverted staggered structure, in which the gate is disposed below the semiconductor layer, while the source and drain 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 may have a structure substantially the same as that of the driving thin film transistor (Td).

[0166] In one example, the organic light-emitting display device 3000 may include a color filter 3600 that absorbs light generated from an 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 regions. Each of these color filter patterns may be arranged to overlap with each organic layer 4300 of the organic light-emitting diode 4000 to emit light of a wavelength band corresponding to each color filter. The use of the color filter 3600 enables the organic light-emitting display device 3000 to achieve full color.

[0167] For example, when the organic light-emitting display device 3000 is a bottom emission type, the light-absorbing color filter 3600 may be located on a portion of the interlayer insulating layer 3400 corresponding to the organic light-emitting diode 4000. In an alternative embodiment, when the organic light-emitting display device 3000 is a top emission type, the color filter may be located on top of the organic light-emitting diode 4000, that is, on top of the second electrode 4200. For example, the color filter 3600 may be formed to have a thickness of 2 to 5 micrometers.

[0168] In one example, the protection layer 3700 having the drain contact hole 3720 as defined herein exposing the drain electrode 3540 of the driving thin film transistor Td is formed to cover the driving thin film transistor Td.

[0169] On the protective layer 3700 , each first electrode 4100 connected to the drain electrode 3540 of the driving thin film transistor Td through the drain contact hole 3720 is individually formed in each pixel region.

[0170] The first electrode 4100 may serve 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.

[0171] In one example, when the organic light-emitting display device 3000 is 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 be made of one of aluminum (Al), silver (Ag), nickel (Ni), and aluminum-palladium-copper (APC) alloy.

[0172] A bank layer 3800 is formed on the protective layer 3700 to cover the edge of the first electrode 4100. The bank layer 3800 exposes the center of the first electrode 4100 corresponding to the pixel area.

[0173] An organic layer 4300 is formed on the first electrode 4100. If necessary, the organic light emitting diode 4000 may have a series structure. Figures 2 to 4 and the above description thereof.

[0174] The second electrode 4200 is formed on the substrate 3010 on which the organic layer 4300 is formed. The second electrode 4200 is arranged on the entire surface of the display area and is made of a conductive material with a relatively small work function value and can serve as a negative electrode (cathode). For example, the second electrode 4200 can be made of one of aluminum (Al), magnesium (Mg), and an aluminum-magnesium alloy (Al-Mg).

[0175] The first electrode 4100 , the organic layer 4300 , and the second electrode 4200 constitute an organic light emitting diode 4000 .

[0176] An encapsulation film 3900 is formed on the second electrode 4200 to prevent external moisture from penetrating into the organic light emitting diode 4000. Figure 4 Although not explicitly shown in FIG, the encapsulation film 3900 may have a three-layer structure in which a first inorganic layer, an organic layer, and an inorganic layer are sequentially stacked. However, the present disclosure is not limited thereto.

[0177] Hereinafter, the preparation examples and embodiments of the present disclosure will be described. However, the following embodiments are merely examples of the present disclosure. The present disclosure is not limited thereto.

[0178] <Preparation Example>

[0179] [Preparation of Compound A1]

[0180]

[0181] Preparation of compound A1-1

[0182] In a reaction vessel, ethyl 2-bromo-6-chlorobenzoate (30 g, 113.84 mmol), benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol), Pd(PPh3)4 (6.58 g, 5.69 mmol) and K2CO3 (47.20 g, 341.53 mmol) were dissolved in 1,4-dioxane (500 ml) and distilled water (100 ml), and the mixture was refluxed for 12 hours. After the reaction was completed, the temperature was lowered to room temperature and then extracted with dichloromethane and distilled water. Magnesium sulfate was added to the organic layer and filtered to remove the moisture therein, and then the solvent was removed therefrom under reduced pressure. Column chromatography was performed with n-hexane and dichloromethane to obtain compound A1-1 (28.1 g, yield 82%).

[0183] MS (m / z): 300.06

[0184] Preparation of compound A1-2

[0185] A1-1 (28.1 g, 93.44 mmol) was dissolved in THF (400 ml) in a reaction vessel, and a 1.6 M solution of MeMgBr in diethyl ether (175 ml, 280.31 mmol) was added dropwise at -78°C for 1 hour, followed by stirring for 12 hours. NH4Cl was added thereto to terminate the reaction, and the mixture was stirred at room temperature for 30 minutes, then extracted with dichloromethane and distilled water. MgSO4 was added to the organic layer and filtered to remove the moisture therein, and then the solvent was removed therefrom under reduced pressure. Column chromatography was performed with n-hexane and dichloromethane. Thus, compound A1-2 (24.38 g, 91% yield) was obtained.

[0186] MS(m / z):286.08

[0187] Preparation of compound A1-3

[0188] A1-2 (24.38 g, 85.02 mmol) and DMF (500 ml) were placed in a reaction vessel, and BF3OEt2 (12.07 g, 85.02 mmol) was added dropwise thereto at 0°C for 1 hour, followed by stirring at room temperature for 1 hour. NaHCO3 was added thereto to terminate the reaction, followed by extraction with dichloromethane and distilled water. MgSO4 was added to the organic layer and filtered to remove moisture, followed by removal of the solvent under reduced pressure. Column chromatography was performed using n-hexane and dichloromethane. Compound A1-3 (16.91 g, 74% yield) was obtained.

[0189] MS(m / z):286.08

[0190] Preparation of compound A1

[0191] In a reaction vessel, A1-3 (16.91 g, 62.92 mmol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bis(1,3,2-dioxaborolane) (19.25 g, 75.51 mmol), Pd(dba)2 (3.63 g, 6.29 mmol), Sphos (5.17 g, 12.58 mmol) and KOAc (18.53 g, 188.77 mmol) were dissolved in 1,4-dioxane (500 ml), and the mixture was refluxed for 12 hours. After the reaction was completed, the temperature was lowered to room temperature, and then extracted with dichloromethane and distilled water. MgSO4 was added to the organic layer and filtered to remove the moisture therein, and then the solvent was removed therefrom under reduced pressure. Column chromatography was performed with n-hexane and dichloromethane to obtain compound A1 (18.81 g, yield 83%).

[0192] MS(m / z):360.19

[0193] [Preparation of Compound A2]

[0194]

[0195] Preparation of compound A2-1

[0196] Compound A2-1 (28.85 g, yield 80%) was obtained by the same method as the preparation method of compound A1-1, except that benzo[b]thiophen-2-ylboronic acid (24.32 g, 136.61 mmol) was used instead of benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol).

[0197] MS(m / z):316.03

[0198] Preparation of compound A2-2

[0199] Compound A2-2 (24.54 g, yield 89%) was obtained by the same method as that of compound A1-2, except that A2-1 (28.85 g, 91.06 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0200] MS(m / z):302.05

[0201] Preparation of compound A2-3

[0202] Compound A2-3 (17.31 g, yield 75%) was obtained by the same method as that of compound A1-3, except that A2-2 (24.54 g, 81.04 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0203] MS(m / z):284.04

[0204] Preparation of compound A2

[0205] Compound A2 (19.44 g, yield 85%) was obtained by the same method as that of compound A1, except that A2-3 (17.31 g, 60.78 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0206] MS(m / z):376.17

[0207] [Preparation of Compound A3]

[0208]

[0209] Preparation of compound A3-1

[0210] The compound A3-1 (31.25 g, yield 84%) was obtained by the same method as the preparation method of compound A1-1, except that 1,1-dimethyl-1H-inden-2-ylboronic acid (25.69 g, 136.61 mmol) was used instead of benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol).

[0211] MS(m / z):326.11

[0212] Preparation of compound A3-2

[0213] Compound A3-2 (27.82 g, yield 93%) was obtained by the same method as that of compound A1-2, except that A3-1 (31.25 g, 95.63 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0214] MS(m / z):312.13

[0215] Preparation of compound A3-3

[0216] Compound A3-3 (20.45 g, yield 78%) was obtained in the same manner as compound A1-3, except that A3-2 (32.76 g, 88.93 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0217] MS(m / z):294.12

[0218] Preparation of compound A3

[0219] Compound A3 (23.32 g, yield 87%) was obtained in the same manner as compound A1, except that A3-3 (20.45 g, 69.37 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0220] MS(m / z):386.33

[0221] [Preparation of Compound A4]

[0222]

[0223] Preparation of compound A4-1

[0224] Compound A4-1 (27.73 g, yield 81%) was obtained in the same manner as compound A1-1, except that ethyl 2-bromo-3-chlorobenzoate (30 g, 113.84 mmol) was used instead of ethyl 2-bromo-6-chlorobenzoate (30 g, 113.84 mmol).

[0225] MS (m / z): 300.06

[0226] Preparation of compound A4-2

[0227] Compound A4-2 (23.80 g, yield 90%) was obtained in the same manner as compound A1-2, except that A4-1 (27.73 g, 92.21 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0228] MS(m / z):286.08

[0229] Preparation of compound A4-3

[0230] Compound A4-3 (16.73 g, yield 75%) was obtained in the same manner as compound A1-3, except that A4-2 (23.80 g, 82.99 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0231] MS(m / z):268.74

[0232] Preparation of compound A4

[0233] Compound A4 (19.19 g, yield 84%) was obtained in the same manner as compound A1, except that A4-3 (16.73 g, 63.42 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0234] MS(m / z):360.19

[0235] [Preparation of Compound A5]

[0236]

[0237] Preparation of compound A5-1

[0238] Compound A5-1 (29.93 g, yield 83%) was obtained by the same method as the preparation method of compound A1-1, except that 2-bromo-3-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzo[b]thiophene-2-ylboronic acid (24.32 g, 136.61 mmol) were used instead of 2-bromo-6-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol), respectively.

[0239] MS(m / z):316.03

[0240] Preparation of compound A5-2

[0241] Compound A5-2 (24.32 g, yield 85%) was obtained in the same manner as compound A1-2, except that A5-1 (29.93 g, 94.49 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0242] MS(m / z):302.05

[0243] Preparation of compound A5-3

[0244] Compound A5-3 (16.24 g, yield 71%) was obtained in the same manner as compound A1-3, except that A5-2 (24.32 g, 80.32 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0245] MS(m / z):284.04

[0246] Preparation of compound A5

[0247] Compound A5 (17.17 g, yield 80%) was obtained by the same method as that of compound A1, except that A5-3 (16.24 g, 57.02 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0248] MS(m / z):376.17

[0249] [Preparation of Compound A6]

[0250]

[0251] Preparation of compound A6-1

[0252] Compound A6-1 (34.73 g, yield 85%) was obtained by the same method as the preparation method of compound A1-1, except that 2-bromo-3-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and 5-isopropylbenzo[b]thiophen-2-ylboronic acid (30.07 g, 136.61 mmol) were used to replace 2-bromo-6-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol), respectively.

[0253] MS(m / z):350.08

[0254] Preparation of compound A6-2

[0255] Compound A6-2 (25.70 g, yield 77%) was obtained by the same method as that of compound A1-2, except that A6-1 (34.73 g, 96.77 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0256] MS(m / z):344.10

[0257] Preparation of compound A6-3

[0258] Compound A6-3 (15.83 g, yield 65%) was obtained in the same manner as compound A1-3, except that A6-2 (25.70 g, 74.51 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0259] MS(m / z):326.09

[0260] Preparation of Compound A6

[0261] Compound A6 (16.41 g, yield 81%) was obtained in the same manner as compound A1, except that A6-3 (15.83 g, 48.43 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0262] MS(m / z):418.21

[0263] [Preparation of Compound A7]

[0264]

[0265] Preparation of compound A7-1

[0266] Compound A7-1 (36.93 g, yield 87%) was obtained by the same method as the preparation method of compound A1-1, except that 2-bromo-3-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and 5-isobutylbenzo[b]thiophen-2-ylboronic acid (31.98 g, 136.61 mmol) were used instead of 2-bromo-6-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol), respectively.

[0267] MS(m / z):372.10

[0268] Preparation of compound A7-2

[0269] Compound A7-2 (29.86 g, yield 84%) was obtained in the same manner as compound A1-2, except that A7-1 (36.93 g, 99.04 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0270] MS(m / z):358.12

[0271] Preparation of compound A7-3

[0272] Compound A7-3 (22.12 g, yield 78%) was obtained in the same manner as compound A1-3, except that A7-2 (29.86 g, 83.20 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0273] MS(m / z):340.11

[0274] Preparation of Compound A7

[0275] Compound A7 (22.45 g, yield 80%) was obtained in the same manner as compound A1, except that A7-3 (22.12 g, 64.89 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0276] MS(m / z):432.23

[0277] [Preparation of Compound A8]

[0278]

[0279] Preparation of compound A8-1

[0280] Except that 2-bromo-4-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzo[b]thiophene-2-ylboronic acid (24.32 g, 136.61 mmol) were used instead of 2-bromo-6-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol), respectively, compound A8-1 (29.93 g, yield 83%) was obtained by the same method as the preparation method of compound A1-1.

[0281] MS(m / z):316.03

[0282] Preparation of compound A8-2

[0283] Compound A8-2 (23.46 g, yield 82%) was obtained in the same manner as compound A1-2, except that A8-1 (29.93 g, 94.49 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0284] MS(m / z):302.05

[0285] Preparation of compound A8-3

[0286] Compound A8-3 (17.0 g, yield 77%) was obtained in the same manner as compound A1-3, except that A8-2 (23.46 g, 77.48 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0287] MS(m / z):284.04

[0288] Preparation of Compound A8

[0289] Compound A8 (17.51 g, yield 78%) was obtained in the same manner as compound A1, except that A8-3 (17.0 g, 59.66 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0290] MS(m / z):376.17

[0291] [Preparation of Compound A9]

[0292]

[0293] Preparation of compound A9-1

[0294] Compound A9-1 (29.57 g, yield 82%) was obtained by the same method as the preparation method of compound A1-1, except that 2-bromo-5-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzo[b]thiophene-2-ylboronic acid (24.32 g, 136.61 mmol) were used instead of 2-bromo-6-chlorobenzoic acid ethyl ester (30 g, 113.84 mmol) and benzofuran-2-ylboronic acid (22.1 g, 136.61 mmol), respectively.

[0295] MS(m / z):316.03

[0296] Preparation of compound A9-2

[0297] Compound A9-2 (24.31 g, yield 86%) was obtained in the same manner as compound A1-2, except that A9-1 (29.57 g, 93.35 mmol) was used instead of A1-1 (28.1 g, 93.44 mmol).

[0298] MS(m / z):302.05

[0299] Preparation of compound A9-3

[0300] Compound A9-3 (18.75 g, yield 82%) was obtained by the same method as the preparation method of compound A1-3, except that A9-2 (24.31 g, 80.28 mmol) was used instead of A1-2 (24.38 g, 85.02 mmol).

[0301] MS(m / z):284.04

[0302] Preparation of Compound A9

[0303] Compound A9 (20.81 g, yield 84%) was obtained by the same method as that of compound A1, except that A9-3 (18.75 g, 65.83 mmol) was used instead of A1-3 (16.91 g, 62.92 mmol).

[0304] MS(m / z):376.17

[0305] [Preparation of Compounds L1 to L24]

[0306] Preparation of compound L1

[0307]

[0308] In a reaction vessel, SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol), A1 (18.04 g, 50.67 mmol), Pd (PPh 3) 4 (2.63 g, 2.28 mmol) and K 2 CO 3 (18.87 g, 136.54 mmol) were dissolved in 1,4-dioxane (300 ml) and distilled water (100 ml), and the mixture was refluxed for 12 hours. After the reaction was completed, the temperature was lowered to room temperature, and then extracted with dichloromethane and distilled water. MgSO 4 was added to the organic layer and filtered to remove the moisture therein, and then the solvent was removed therefrom under reduced pressure. Column chromatography was performed with n-hexane and dichloromethane to obtain compound L1 (15.01 g, yield 79%).

[0309] MS(m / z):417.21

[0310] Preparation of compound L2

[0311] Compound L2 (14.71 g, yield 75%) was obtained by the same method as the preparation method of compound L1, except that SM2 (2-chloro-4,5,7-trimethylquinoline) (10 g, 48.62 mmol) was used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol).

[0312] MS(m / z):403.19

[0313] Preparation of compound L3

[0314] Compound L3 (16.47 g, yield 78%) was obtained by the same method as the preparation method of compound L1, except that SM3 (2-chloro-6-methylquinoline) (10 g, 56.30 mmol) was used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol).

[0315] MS(m / z):375.16

[0316] Preparation of compound L4

[0317] Compound L4 (14.80 g, yield 75%) was obtained by the same method as that of compound L1, except that A2 (18.83 g, 50.05 mmol) was used instead of A1 (18.04 g, 50.67 mmol).

[0318] MS(m / z):433.19

[0319] Preparation of compound L5

[0320] Compound L5 (15.91 g, yield 78%) was obtained by the same method as the preparation method of compound L1, except that SM2 (2-chloro-4,5,7-trimethylquinoline) (10 g, 48.62 mmol) and A2 (20.13 g, 53.48 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0321] MS(m / z):419.17

[0322] Preparation of compound L6

[0323] Compound L6 (15.79 g, yield 80%) was obtained by the same method as the preparation method of compound L1, except that SM4 (4-tert-butyl-2-chloroquinoline) (10 g, 45.51 mmol) and A2 (18.84 g, 50.07 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0324] MS(m / z):433.19

[0325] Preparation of compound L7

[0326] Compound L7 (17.13 g, yield 79%) was obtained by the same method as the preparation method of compound L1, except that SM5 (2-chloro-5,7-dimethylquinoline) (10 g, 52.18 mmol) and A3 (22.17 g, 57.39 mmol) were used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0327] MS(m / z):415.23

[0328] Preparation of compound L8

[0329] Compound L8 (16.66 g, yield 82%) was obtained by the same method as the preparation method of compound L1, except that SM5 (2-chloro-5,7-dimethylquinoline) (10 g, 52.18 mmol) and A4 (20.68 g, 57.39 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0330] MS(m / z):389.18

[0331] Preparation of compound L9

[0332] Compound L9 (17.77 g, yield 77%) was obtained by the same method as the preparation method of compound L1, except that SM6 (2-chloroquinoline) (10 g, 61.12 mmol) and A5 (25.30 g, 67.24 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0333] MS(m / z):377.12

[0334] Preparation of compound L10

[0335] Compound L10 (13.77 g, yield 75%) was obtained by the same method as the preparation method of compound L1, except that SM2 (2-chloro-4,5,7-trimethylquinoline) (10 g, 48.62 mmol) and A6 (22.38 g, 53.48 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0336] MS(m / z):377.12

[0337] Preparation of compound L11

[0338] Compound L11 (17.11 g, yield 74%) was obtained by the same method as the preparation method of compound L1, except that SM2 (2-chloro-4,5,7-trimethylquinoline) (10 g, 48.62 mmol) and A7 (23.13 g, 53.48 mmol) were used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0339] MS(m / z):475.23

[0340] Preparation of compound L12

[0341] Compound L12 (17.63 g, yield 80%) was obtained by the same method as the preparation method of compound L1, except that SM3 (2-chloro-6-methylquinoline) (10 g, 56.30 mmol) and A5 (23.30 g, 61.93 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0342] MS(m / z):391.14

[0343] Preparation of compound L13

[0344] Compound L13 (15.30 g, yield 75%) was obtained by the same method as the preparation method of compound L1, except that SM2 (2-chloro-4,5,7-trimethylquinoline) (10 g, 48.62 mmol) and A8 (20.13 g, 53.48 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0345] MS(m / z):419.17

[0346] Preparation of compound L14

[0347] Compound L14 (12.92 g, yield 77%) was obtained by the same method as the preparation method of compound L1, except that SM7 (3-bromo-6-isopropylisoquinoline) (10 g, 40.0 mmol) and A2 (16.54 g, 43.98 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0348] MS(m / z):419.17

[0349] Preparation of compound L15

[0350] Compound L15 (14.61 g, yield 73%) was obtained by the same method as the preparation method of compound L1, except that SM8 (6-chlorophenanthridine) (10 g, 46.80 mmol) and A2 (19.37 g, 51.48 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0351] MS(m / z):427.14

[0352] Preparation of compound L16

[0353] Compound L16 (14.94 g, yield 78%) was obtained by the same method as the preparation method of compound L1, except that SM9 (1-chloro-6-isobutyl-3-methylisoquinoline) (10 g, 42.78 mmol) and A2 (17.71 g, 47.06 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0354] MS(m / z):447.20

[0355] Preparation of compound L17

[0356] Compound L17 (17.48 g, yield 76%) was obtained by the same method as the preparation method of compound L1, except that SM10 (2-chloroquinazoline) (10 g, 60.76 mmol) and A2 (25.15 g, 66.83 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0357] MS(m / z):378.12

[0358] Preparation of compound L18

[0359] Compound L18 (16.01 g, yield 79%) was obtained by the same method as the preparation method of compound L1, except that SM11 (2-chloro-5,7-dimethylquinazoline) (10 g, 51.91 mmol) was used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol).

[0360] MS(m / z):390.17

[0361] Preparation of compound L19

[0362] Compound L19 (15.18 g, yield 77%) was obtained by the same method as the preparation method of compound L1, except that SM12 (2-chlorobenzofurano[2,3-b]pyridine) (10 g, 49.11 mmol) was used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol).

[0363] MS(m / z):401.14

[0364] Preparation of compound L20

[0365] Compound L20 (16.93 g, yield 75%) was obtained by the same method as the preparation method of compound L1, except that SM12 (2-chlorobenzofuran[2,3-b]pyridine) (10 g, 49.11 mmol) and A6 (22.60 g, 54.02 mmol) were used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0366] MS(m / z):459.17

[0367] Preparation of compound L21

[0368] Compound L21 (16.16 g, yield 79%) was obtained by the same method as the preparation method of compound L1, except that SM13 (4-chlorobenzofuro[3,2-d]pyrimidine) (10 g, 48.87 mmol) and A2 (20.23 g, 53.76 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0369] MS(m / z):418.11

[0370] Preparation of compound L22

[0371] Compound L22 (15.17 g, yield 74%) was obtained by the same method as the preparation method of compound L1, except that SM14 (2-chlorobenzofuran[3,2-b]pyridine) (10 g, 49.11 mmol) and A9 (20.33 g, 54.02 mmol) were used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0372] MS(m / z):417.12

[0373] Preparation of compound L23

[0374] Compound L23 (14.23 g, yield 70%) was obtained by the same method as the preparation method of compound L1, except that SM15 (2-chloro-5,7-dimethylquinoline) (10 g, 52.18 mmol) was used instead of SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol).

[0375] MS(m / z):389.18

[0376] Preparation of compound L24

[0377] Compound L24 (15.30 g, yield 75%) was obtained by the same method as the preparation method of compound L1, except that SM16 (2-chloro-6-isopropylquinoline) (10 g, 48.62 mmol) and A2 (19.27 g, 53.48 mmol) were used to replace SM1 (2-chloro-6-isobutylquinoline) (10 g, 45.51 mmol) and A1 (18.04 g, 50.67 mmol), respectively.

[0378] MS(m / z):419.17

[0379] <Preparation of Organometallic Compounds>

[0380] (1) Preparation of Compound 40

[0381]

[0382] Preparation of compound M1

[0383] L1 (10 g, 23.95 mmol), 200 ml of 1,4-dioxane, and 50 ml of distilled water were placed in a reaction vessel and bubbling with nitrogen for 1 hour. IrCl3xH2O (3.80 g, 8.44 mmol) was then added and the mixture was refluxed for 24 hours. After the reaction was completed, the temperature was slowly lowered to room temperature, and the resulting solid was filtered. The filtered solid was washed with methanol and dried to obtain intermediate M1 (5.10 g, 57% yield).

[0384] Preparation of Compound 40

[0385] Intermediate M1 (5.10 g, 2.41 mmol), 3,7-diethyl-3,7-dimethylnonane-4,6-dione (1.73 g, 7.22 mmol), Na2CO3 (5.10 g, 48.11 mmol) and 100 ml of 1,4-dioxane were added to a reaction vessel, and the mixture was refluxed for 24 hours under a nitrogen atmosphere. After the reaction was completed, dichloromethane was added to the reaction mixture to dissolve the reaction mixture, and then the reaction mixture was extracted with dichloromethane and distilled water. The water in the organic layer was removed with MgSO4, and after filtration, the solvent was removed under reduced pressure. Column chromatography was performed with n-hexane and dichloromethane. Thus, compound 40 (2.43 g, yield 40%) was obtained.

[0386] MS(m / z):1264.57

[0387] (2) Preparation of Compound 45

[0388] Intermediate M2 (4.97 g, yield 55%) was obtained by the same method as that of intermediate M1, except that L2 (10 g, 24.78 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0389] Compound 45 (2.38 g, yield 48%) was obtained by the same method as that of compound 40, except that M2 (4.97 g, 2.41 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0390] MS(m / z):1236.54

[0391] (3) Preparation of Compound 98

[0392]

[0393] Intermediate M3 (4.98 g, yield 54%) was obtained by the same method as that of intermediate M1, except that L3 (10 g, 26.63 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0394] Then, 2-bromopropane (1.25 g, 10.19 mmol) and 100 ml of tetrahydrofuran were added to the reaction vessel under nitrogen, the temperature was lowered to -78°C, and then n-butyllithium (4.08 ml, 2.5 M solution in hexane) was slowly added. After 30 minutes, N,N'-diisopropylcarbodiimide (1.29 g, 10.19 mmol) was slowly added while maintaining the temperature, and the mixture was stirred for 30 minutes. The reaction mixture was added to a reaction vessel in which M3 (4.98 g, 2.55 mmol) was dissolved in 200 ml of tetrahydrofuran, and the mixture was stirred at 80°C for 8 hours. The temperature of the reaction mixture was lowered to room temperature, volatile substances were removed therefrom, and it was recrystallized using tetrahydrofuran / pentane and dichloromethane / hexane to obtain compound 98 (2.26 g, 50% yield).

[0395] MS(m / z):1110.44

[0396] (4) Preparation of Compound 124

[0397] Intermediate M4 (4.66 g, yield 52%) was obtained by the same method as that of intermediate M1, except that L4 (10 g, 23.06 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0398] Compound 124 (1.97 g, yield 52%) was obtained by the same method as the preparation method of compound 40, except that M4 (4.66 g, 2.13 mmol) and pentane-2,4-dione (0.64 g, 6.39 mmol) were used to replace M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonane-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0399] MS(m / z):1156.36

[0400] (5) Preparation of Compound 153

[0401] Intermediate M5 (4.25 g, yield 47%) was obtained by the same method as that of intermediate M1, except that L5 (10 g, 23.83 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0402] Compound 153 (1.98 g, yield 45%) was obtained by the same method as that of compound 40, except that M5 (4.25 g, 2.00 mmol) and 3,7-diethylnonyl-4,6-dione (1.27 g, 5.99 mmol) were used instead of M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonyl-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0403] MS(m / z):1240.46

[0404] (6) Preparation of Compound 160

[0405] Intermediate M4 (4.68 g, yield 52%) was obtained by the same method as that of intermediate M1, except that L4 (10 g, 23.06 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0406] Compound 160 (2.22 g, yield 43%) was obtained by the same method as that of compound 40, except that M4 (4.68 g, 2.14 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0407] MS(m / z):1296.52

[0408] (7) Preparation of Compound 163

[0409] Intermediate M6 (4.97 g, yield 55%) was obtained by the same method as that of intermediate M1, except that L6 (10 g, 23.06 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0410] Compound 163 (2.36 g, yield 49%) was obtained by the same method as that of compound 40, except that M6 (4.97 g, 2.27 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0411] MS(m / z):1296.52

[0412] (8) Preparation of Compound 272

[0413] Intermediate M7 (4.20 g, yield 46%) was obtained by the same method as that of intermediate M1, except that L7 (10 g, 24.06 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0414] Compound 272 (1.96 g, yield 47%) was obtained by the same method as that of compound 40, except that M7 (4.20 g, 1.99 mmol) and 3,7-diethylnonyl-4,6-dione (1.27 g, 5.97 mmol) were used to replace M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonyl-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0415] MS(m / z):1232.58

[0416] (9) Preparation of Compound 380

[0417] Intermediate M8 (4.37 g, yield 47%) was obtained by the same method as that of intermediate M1, except that L8 (10 g, 25.67 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0418] Compound 380 (2.00 g, yield 54%) was obtained by the same method as the preparation method of compound 40, except that M8 (4.37 g, 2.17 mmol) and 2,2,6,6-tetramethylheptane-3,5-dione (1.20 g, 6.52 mmol) were used instead of M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonane-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0419] MS(m / z):1152.44

[0420] (10) Preparation of Compound 433

[0421] Intermediate M9 (4.60 g, yield 49%) was obtained by the same method as that of intermediate M1, except that L9 (10 g, 26.49 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0422] Compound 433 (2.17 g, yield 51%) was obtained by the same method as that of compound 40, except that M9 (4.60 g, 2.35 mmol) and 3,7-diethylnonyl-4,6-dione (1.49 g, 7.04 mmol) were used instead of M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonyl-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0423] MS(m / z):1156.36

[0424] (11) Preparation of Compound 443

[0425] Intermediate M10 (4.69 g, yield 52%) was obtained by the same method as that of intermediate M1, except that L10 (10 g, 21.66 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0426] Compound 443 (2.16 g, yield 44%) was obtained by the same method as that of compound 40, except that M10 (4.69 g, 2.04 mmol) and 3,7-diethylnonyl-4,6-dione (1.30 g, 6.12 mmol) were used to replace M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonyl-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0427] MS(m / z):1324.55

[0428] (12) Preparation of Compound 492

[0429]

[0430] Intermediate M11 (4.95 g, yield 55%) was obtained by the same method as that of intermediate M1, except that L1 (10 g, 21.02 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0431] Then, M11 (4.95 g, 2.10 mmol) and 100 ml of THF were placed in a reaction vessel under nitrogen, and LA1 (3.67 g, 12.6 mmol) dissolved in THF was slowly added, followed by stirring at room temperature for 8 hours. After the reaction was completed, THF was removed, and extraction was performed with toluene. The solvent was then removed, and diethyl ether was added. Thus, compound 492 (2.34 g, 43% yield) was obtained.

[0432] MS(m / z):1393.65

[0433] (13) Preparation of Compound 518

[0434] Intermediate M12 (5.45 g, yield 58%) was obtained by the same method as that of intermediate M1, except that L12 (10 g, 25.54 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0435] Compound 518 (2.64 g, yield 47%) was obtained by the same method as that of compound 98, except that M12 (5.45 g, 2.70 mmol) and N,N'-methanediyldicyclohexylamine (2.23 g, 10.80 mmol) were used instead of M3 (4.98 g, 2.55 mmol) and N,N'-diisopropylcarbodiimide (1.29 g, 10.19 mmol), respectively.

[0436] MS(m / z):1222.46

[0437] (14) Preparation of Compound 623

[0438] Intermediate M13 (4.54 g, yield 49%) was obtained by the same method as that of intermediate M1, except that L13 (10 g, 23.83 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0439] Compound 623 (2.17 g, yield 50%) was obtained by the same method as that of compound 40, except that M13 (4.54 g, 2.13 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0440] MS(m / z):1268.49

[0441] (15) Preparation of Compound 674

[0442] Intermediate M14 (4.65 g, yield 50%) was obtained by the same method as that of intermediate M1, except that L14 (10 g, 23.83 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0443] Compound 674 (2.17 g, yield 53%) was obtained by the same method as that of compound 40, except that M14 (4.65 g, 2.18 mmol) and 3,7-diethylnonyl-4,6-dione (1.39 g, 6.55 mmol) were used to replace M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonyl-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0444] MS(m / z):1240.46

[0445] (16) Preparation of Compound 681

[0446] Intermediate M15 (4.74 g, yield 51%) was obtained by the same method as that of intermediate M1, except that L15 (10 g, 23.39 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0447] Compound 681 (2.20 g, yield 51%) was obtained by the same method as the preparation method of compound 40, except that M15 (4.74 g, 2.19 mmol) and 3,7-diethylnonyl-4,6-dione (1.40 g, 6.57 mmol) were used to replace M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonyl-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0448] MS(m / z):1256.40

[0449] (17) Preparation of Compound 692

[0450] Intermediate M16 (4.14 g, yield 44%) was obtained by the same method as that of intermediate M1, except that L16 (10 g, 23.06 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0451] Compound 692 (1.94 g, yield 49%) was obtained by the same method as that of compound 40, except that M16 (4.14 g, 1.87 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0452] MS(m / z):1296.52

[0453] (18) Preparation of Compound 749

[0454] Intermediate M17 (4.60 g, yield 48%) was obtained by the same method as that of intermediate M1, except that L17 (10 g, 26.42 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0455] Compound 749 (2.22 g, yield 46%) was obtained by the same procedure as that of compound 40, except that M17 (4.60 g, 2.34 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0456] MS(m / z):1186.39

[0457] (19) Preparation of Compound 764

[0458] Intermediate M18 (4.30 g, yield 45%) was obtained by the same method as that of intermediate M1, except that L18 (10 g, 24.91 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0459] Compound 764 (2.07 g, yield 48%) was obtained by the same procedure as that of compound 40, except that M18 (4.30 g, 2.13 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0460] MS(m / z):1210.49

[0461] (20) Preparation of Compound 781

[0462] Intermediate M19 (4.00 g, yield 42%) was obtained by the same method as that of intermediate M1, except that L19 (10 g, 24.91 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0463] Compound 781 (1.92 g, yield 54%) was obtained by the same procedure as that of compound 40, except that M19 (4.00 g, 1.94 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0464] MS(m / z):1232.43

[0465] (21) Preparation of Compound 791

[0466] Intermediate M20 (4.55 g, yield 49%) was obtained by the same method as that of intermediate M1, except that L20 (10 g, 21.76 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0467] Compound 791 (2.14 g, yield 55%) was obtained by the same procedure as that of compound 40, except that M20 (4.55 g, 1.99 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0468] MS(m / z):1348.48

[0469] (22) Preparation of Compound 809

[0470] Intermediate M21 (4.93 g, yield 52%) was obtained by the same method as that of intermediate M1, except that L21 (10 g, 23.89 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0471] Compound 809 (2.35 g, yield 52%) was obtained by the same procedure as that of compound 40, except that M21 (4.93 g, 2.32 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0472] MS(m / z):1266.38

[0473] (23) Preparation of Compound 832

[0474] Intermediate M22 (4.85 g, yield 51%) was obtained by the same method as that of intermediate M1, except that L22 (10 g, 23.95 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0475] Compound 832 (2.31 g, 45% yield) was obtained by the same procedure as that of compound 40, except that M22 (4.85 g, 2.29 mmol) was used instead of M1 (5.10 g, 2.41 mmol).

[0476] MS(m / z):1264.39

[0477] (24) Preparation of Compound 844

[0478] Intermediate M23 (4.79 g, yield 52%) was obtained by the same method as that of intermediate M1, except that L23 (10 g, 25.67 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0479] Compound 844 (2.77 g, yield 47%) was obtained by the same method as that of compound 40, except that M23 (4.79 g, 2.41 mmol) and 3,7-diisopropyl-2,8-dimethylnonane-4,6-dione (1.92 g, 7.15 mmol) were used to replace M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonanone (1.73 g, 7.22 mmol), respectively.

[0480] MS(m / z):1236.60

[0481] (25) Preparation of Compound 875

[0482] Intermediate M24 (4.35 g, yield 48%) was obtained by the same method as that of intermediate M1, except that L24 (10 g, 23.83 mmol) was used instead of L1 (10 g, 23.95 mmol).

[0483] Compound 875 (2.44 g, 45% yield) was obtained by the same method as that of compound 40, except that M24 (4.35 g, 2.04 mmol) and 3,7-diisopropyl-2,3,7,8-tetramethylnonane-4,6-dione (0.64 g, 6.39 mmol) were used instead of M1 (5.10 g, 2.41 mmol) and 3,7-diethyl-3,7-dimethylnonane-4,6-dione (1.73 g, 7.22 mmol), respectively.

[0484] MS(m / z):1324.55

[0485] <Example 1>

[0486] Clean the coating with a thickness of A glass substrate with an ITO (indium tin oxide) thin film was then ultrasonically cleaned with a solvent such as isopropyl alcohol or acetone. The glass substrate was then dried. Thus, an ITO transparent electrode was formed. HI-1, a hole injection material, was deposited on the ITO transparent electrode by thermal vacuum deposition. Thus, a hole injection layer with a thickness of 60 nm was formed. Then, NPB, a hole transport material, was deposited on the hole injection layer by thermal vacuum deposition. Thus, a hole transport layer with a thickness of 80 nm was formed. Then, CBP, a host material for the light-emitting layer, was deposited on the hole transport layer by thermal vacuum deposition. Compound 40, as a dopant, was doped into the host material at a doping concentration of 5%. Thus, a light-emitting layer with a thickness of 30 nm was formed. ET-1:Liq (1:1) (30 nm), a material for the electron transport layer and electron injection layer, was deposited on the light-emitting layer. Then, aluminum with a thickness of 100 nm was deposited thereon to form a negative electrode. In this way, an organic light-emitting diode was manufactured.

[0487]

[0488] HI-1 means N1,N1′-([1,1′-biphenyl]-4,4′-diyl)bis(N1,N4,N4-triphenylbenzene-1,4-diamine).

[0489] ET-1 means 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole.

[0490] <Examples 2 to 25 and Comparative Examples 1 to 2>

[0491] Organic light emitting diodes of Examples 2 to 25 and Comparative Examples 1 to 2 were manufactured in the same manner as in Example 1, except that the compounds shown in Tables 1 and 2 below were used instead of Compound 40 as a dopant in Example 1.

[0492] <Performance Evaluation of Organic Light-Emitting Diodes>

[0493] For the organic light emitting diodes prepared according to Examples 1 to 25 and Comparative Examples 1 to 2 of the present disclosure, the measured 2 The operating voltage and efficiency characteristics at current, as well as at 20 mA / cm 2 The lifetime characteristics under accelerated conditions were evaluated. Therefore, the operating voltage (V), EQE (%), and LT95 (%) were measured, and the results are shown in Tables 1 and 2 below. LT95 refers to a lifetime evaluation protocol and means the time required for an organic light emitting diode to lose 5% of its initial luminance.

[0494] In this regard, the performance evaluation values of each of Examples 1 to 21 in Table 1 below are relative values relative to the values of Comparative Example 1. The performance evaluation values of each of Examples 22 to 25 in Table 2 below are relative values relative to the values of Comparative Example 2.

[0495] Table 1

[0496]

[0497] The structure of the dopant material RD-1 as Comparative Example 1 in Table 1 is as follows.

[0498]

[0499] Table 2

[0500]

[0501] The structure of the dopant material RD-2 as Comparative Example 2 in Table 2 is as follows.

[0502]

[0503] As can be seen from the results in Table 1 above, in the organic light-emitting diodes in which the organometallic compounds of Examples 1 to 21 according to the present disclosure are used as dopants for the light-emitting layers of the diodes, the operating voltage of the diodes is reduced, and the external quantum efficiency (EQE) and life (LT95) of the diodes are improved compared to those in Comparative Example 1.

[0504] As can be seen from the results in Table 2 above, in the organic light-emitting diodes in which the organometallic compounds of Examples 22 to 25 according to the present disclosure are used as dopants for the light-emitting layer of the diodes, the operating voltage of the diodes is reduced, and the external quantum efficiency (EQE) and life (LT95) of the diodes are improved compared to those in Comparative Example 2.

[0505] The scope of protection of the present disclosure should be interpreted by the scope of the claims, and all technical concepts within the scope equivalent thereto should be interpreted as included within the scope of the present disclosure. Although the 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 can be implemented in various modified ways without departing from the scope of the technical concept of the present disclosure. Therefore, the embodiments of the present disclosure are not intended to limit the technical concept of the present disclosure, but to describe the present disclosure. The scope of the technical concept of the present disclosure is not limited by the embodiments. Therefore, it should be understood that the above-mentioned embodiments are illustrative and non-restrictive in all aspects. The scope of protection of the present disclosure should be interpreted by the claims, and all technical concepts within the scope of the present disclosure should be interpreted as included within the scope of the present disclosure.

Claims

1. An organometallic compound represented by the following chemical formula 1: Wherein in the chemical formula 1, M represents Ir; R represents a cyclic structure fused to a pair selected from a pair of X5 and X6, a pair of X6 and X7, and a pair of X7 and X8; X1 to X4 are each independently selected from one of CR5 and N; Alternatively, two R5s on two adjacent groups of X1 to X4 are connected to each other to form a cyclic structure, wherein the cyclic structure includes one selected from the group consisting of a substituted or unsubstituted C6-C30 aryl group and an unsubstituted C3-C30 heteroaryl group; Y represents one selected from the group consisting of CR6R7, O, and S; X5 to X8 each independently represent CH; R1 to R4 each independently represent one selected from the group consisting of hydrogen, isopropyl, and 2-methylpropyl; R5 each independently represents one selected from the group consisting of hydrogen, unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, alkoxy, acyl, and carboxylic acid; R6 to R7 each independently represent an unsubstituted C1-C20 alkyl group; (Z1-Z2) represents a bidentate ligand selected from the group formed; and m is 2, n is 1, and the sum of m and n is the oxidation number of the M.

2. The organometallic compound according to claim 1, wherein the Chemical Formula 1 is one selected from the group consisting of the following Chemical Formulas 2 to 5: In each of the Chemical Formulas 2 to 5, X9 to X 12 Each independently represents one selected from CR9 and N; R9 each independently represents one selected from the group consisting of hydrogen and unsubstituted C1-C20 alkyl; X 13 To X 16 Each independently represents CH; M, Y, X1 to X8, R, R1 to R8, (Z1-Z2), m and n are the same as defined in claim 1.

3. The organometallic compound according to claim 1, wherein the Chemical Formula 1 is one selected from the group consisting of the following Chemical Formulas 6 to 11: In each of the Chemical Formulas 6 to 11, X 17 To X 20 Each independently represents CH; Y1 represents O; M, Y, X1 to X8, R, R1 to R8, (Z1-Z2), m and n are the same as defined in claim 1.

4. The organometallic compound according to claim 1, wherein the compound represented by Chemical Formula 1 comprises one selected from the group consisting of:

5. An organic light-emitting device, comprising: a first electrode; a second electrode facing the first electrode; as well as an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a light-emitting layer, wherein the light emitting layer comprises a dopant material, and Wherein the dopant material comprises the organometallic compound according to claim 1 . The organic light-emitting device according to claim 5 , wherein the light-emitting layer is a red light-emitting layer. The organic light-emitting device according to claim 5 , wherein the light-emitting layer further comprises a host material. 8 . The organic light-emitting device according to claim 5 , wherein the organic layer further comprises at least one selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.

9. An organic light-emitting device, comprising: a first electrode and a second electrode facing each other; as well as a first light emitting stack and a second light emitting stack located between the first electrode and the second electrode, wherein each of the first light-emitting stack and the second light-emitting stack comprises at least one light-emitting layer, wherein at least one of the light-emitting layers is a red phosphorescent light-emitting layer, wherein the red phosphorescent light-emitting layer comprises a dopant material, and Wherein the dopant material comprises the organometallic compound according to claim 1 .

10. An organic light-emitting device, comprising: a first electrode and a second electrode facing each other; as well as a first light emitting stack, a second light emitting stack, and a third light emitting stack located between the first electrode and the second electrode, wherein each of the first light-emitting stack, the second light-emitting stack, and the third light-emitting layer comprises at least one light-emitting layer, wherein at least one of the light-emitting layers is a red phosphorescent light-emitting layer, wherein the red phosphorescent light-emitting layer comprises a dopant material, and Wherein the dopant material comprises the organometallic compound according to claim 1 .

11. An organic light-emitting display device, comprising: substrate; a driving element located on the substrate; as well as An organic light emitting element provided on the substrate and connected to the driving element, The organic light-emitting element comprises the organic light-emitting device according to claim 5 .

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