Novel compound and organic light-emitting element comprising same

Abstract

The present invention provides a novel compound containing a rigid fluorenyl substituent in 1, 10-phenanthroline having lone pair electrons, and an organic light-emitting element comprising the same. When applied to one or more organic layers, including an electron transport layer (ETL), a hole blocking layer (HBL), and an N-type charge generation layer (N-CGL), the novel compound enables the realization of a low-voltage, high-efficiency, long-life organic light-emitting element.

Description

Technical Field

[0001] This invention relates to a novel compound and an organic light-emitting element comprising the same. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are one of the most widely used flat panel display components, and their technology is developing rapidly.

[0003] Generally speaking, organic light-emitting elements have an organic thin film layer containing a light-emitting layer formed between the anode (hole injection electrode) and the cathode (electron injection electrode). The principle is that when holes injected from the anode and electrons injected from the cathode pair up in the light-emitting layer, they disappear and emit light.

[0004] More specifically, the organic light-emitting element is configured to include an organic thin film layer formed between an anode and a cathode, and the organic thin film layer is configured to include a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer sequentially laminated on the anode, and holes injected from the anode and electrons injected from the cathode combine in the light-emitting layer to form excitons, which enter an unstable energy state (excited state) and then return to a stable ground state to emit light.

[0005] In the development of organic light-emitting elements (OLEDs), high efficiency, long lifespan, color purity, color stability under current and voltage variations, and ease of fabrication are crucial. Therefore, research and development of various methods are ongoing. OLED structures can be broadly categorized into single-emitting structures with a single OLED element and stacked structures with two or more OLED elements. Among these, the series-connected structure of stacked two or more OLED elements is the most commonly used method for long-lifespan OLEDs.

[0006] Simultaneously, this series-connected organic light-emitting element incorporates a charge generation layer (CGL) between the light-emitting layers, doubling the current efficiency generated by the light-emitting layers and promoting charge distribution. This charge generation layer generates charges (electrons and holes), further enhancing the current efficiency of the light-emitting layers and promoting charge distribution, thereby preventing voltage spikes and serving multiple functions. This charge generation layer consists of a P-type charge generation layer and an N-type charge generation layer.

[0007] Currently, compounds used in charge generation layers, especially N-type charge generation layers, have increasingly higher requirements for developing high-performance devices, thus necessitating the development of new materials that can exhibit excellent performance. Summary of the Invention

[0008] This invention provides a novel compound in which a rigid fluorenyl substituent is introduced into 1,10-phenanthroline having non-shared electron pairs. When this novel compound is applied to at least one organic layer in an electron transport layer (ETL), a hole blocking layer (HBL), and an N-type charge generation layer (N-CGL), the aim is to provide an organic light-emitting element that can achieve low voltage, high efficiency, and long lifetime.

[0009] Next, we will provide a detailed explanation of the topics mentioned above, as well as the additional topics.

[0010] To address the aforementioned issues, in one embodiment of the present invention, a novel compound represented by the following chemical formula 1 is provided.

[0011] <Chemical Formula 1>

[0012]

[0013] In the chemical formula 1,

[0014] Ring A is phenyl or naphthyl.

[0015] R1 can be, independently, hydrogen, deuterium, halogen, cyano, nitro, nitrile, hydroxyl, thiol, substituted or unsubstituted C0–C50 amino, substituted or unsubstituted C1–C50 alkyl, substituted or unsubstituted C1–C50 alkenyl, substituted or unsubstituted C1–C50 alkoxy, substituted or unsubstituted C1–C50 thioether, substituted or unsubstituted C0–C50 silyl, substituted or unsubstituted C3–C50 cycloalkyl, substituted or unsubstituted... The following groups may be substituted C2-C50 heterocyclic alkyl groups, substituted or unsubstituted C3-C50 cycloalkenyl groups, substituted or unsubstituted C1-C30 phosphinoalkyl groups, substituted or unsubstituted C2-C50 heterocyclic alkenyl groups, substituted or unsubstituted C6-C50 aryl groups, substituted or unsubstituted C6-C50 aryloxy groups, substituted or unsubstituted C2-C50 heteroaryloxy groups, or substituted or unsubstituted C2-C50 heteroaryl groups, wherein adjacent groups may or may not combine to form a substituted or unsubstituted ring.

[0016] L can be a direct bond, a substituted or unsubstituted C6-C50 arylene, or a substituted or unsubstituted C2-C50 heteroarylene.

[0017] R2 through R5 are each independently hydrogen or deuterium, or adjacent groups may or may not combine to form a ring substituted or unsubstituted with one or more deuterium atoms.

[0018] a is an integer from 0 to 7.

[0019] b is an integer from 0 to 3.

[0020] c is an integer from 0 to 6.

[0021] d and e are each independent integers from 0 to 4.

[0022] f is an integer from 0 to 5.

[0023] Furthermore, in one embodiment, the present invention provides an organic light-emitting element comprising the novel compound described above.

[0024] The novel compound according to an embodiment of the present invention is particularly suitable for N-type charge-generating layers because it can be readily combined with dopants such as lithium and ytterbium by introducing 1,10-phenanthroline with non-shared electron pairs, and has excellent thermal stability by introducing rigid fluorene substituents.

[0025] Furthermore, the novel compound according to an embodiment of the present invention has a reverse structure in which 1,10-phenanthroline is bonded to a phenyl or naphthyl group above diphenylfluorene or naphthylphenylfluorene, thus having a lower RE (recombination energy) value compared to the structure bonded to the fluorene below, thereby improving the efficiency of the element.

[0026] Furthermore, the novel compound of one embodiment of the present invention has increased conjugation due to its structure that binds to the N atom of 1,10-phenanthroline at a position (position 2 or 9), resulting in a lower RE value compared to other positions, thereby improving the efficiency of the element.

[0027] Furthermore, by eliminating the introduction of additional functional groups into fluorene, the filling density and refractive index can be increased, thereby extending the lifespan of the component.

[0028] The novel compounds of this invention can be effectively applied to one or more organic layers in the organic layers of an organic light-emitting element, including the electron transport layer (ETL), hole blocking layer (HBL), and N-type charge generation layer (N-CGL). In particular, when applied to the main body of the N-type charge generation layer of a series organic light-emitting element, it can achieve low voltage, high efficiency, and long lifespan of the element.

[0029] Next, we will explain in detail the effects and additional effects described above. Detailed Implementation

[0030] In describing this invention, a detailed description of a related known configuration or function will be omitted if it is determined that such a description may obscure the gist of the invention.

[0031] In this specification, when a part "includes" a component, it does not mean that other components are excluded, but rather that other components may be included, unless otherwise expressly stated.

[0032] In this specification, when it is said that one component is "above" another component, this includes not only the case where one component is in contact with another component, but also the case where there is another component between the two components.

[0033] In describing the components of this invention, terms such as first, second, A, B, (a), (b) may be used. These terms are used only to distinguish a component from other components, and the nature, order, or sequence of the components is not limited by these terms. When describing a component as "connected," "coupled," or "connected" to another component, it should be understood that the component can be directly connected to or connected to another component, but another component can also be "connected," "coupled," or "connected" between each component.

[0034] Examples of substituents in this specification are shown below, but are not limited thereto.

[0035] As used in this article, "substitution" refers to the replacement of a hydrogen atom bonded to a carbon atom in a compound by another substituent. The substitution position is not particularly limited, as long as it is a substitutable position. When there are two or more substituents, the substituents can be the same or different.

[0036] In this specification, "substituted or unsubstituted" means substituted by one or more substituents selected from deuterium, halogen, cyano, nitro, nitrile, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, sulfide, aryloxy, heteroaryloxy, thio, amino, silyl, phosphonyl oxide, aryl, and heteroaryl, or substituted by two or more substituents selected from the above groups linked together, or without substituents, and the selected substituents may or may not be linked to each other to form a ring. An example of a substituent with two or more substituents linked together is biphenyl. That is, biphenyl can correspond to an aryl group, simultaneously correspond to a substituent with two phenyl links, and simultaneously correspond to an aryl group with one phenyl substitution.

[0037] In this specification, alkyl groups can be straight-chain or branched chains having 1 to 60 carbon atoms, and specific examples include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl. Specifically, the number of carbon atoms in an alkyl group can be from 1 to 30, more specifically from 1 to 20.

[0038] In this specification, the alkenyl group can be a straight-chain or branched chain having 2 to 60 carbon atoms, and specific examples include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbene, styryl, etc. Specifically, the number of carbon atoms in the alkenyl group can be 2 to 30, more specifically 2 to 20.

[0039] In this specification, the alkynyl group can be a straight chain or a branched chain having 2 to 60 carbon atoms. Specifically, the number of carbon atoms in the alkynyl group can be 2 to 30, more specifically 2 to 20.

[0040] In this specification, an alkoxy group can be a straight-chain, branched, or cyclic chain having 1 to 60 carbon atoms. Specific examples include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy, etc. Specifically, the number of carbon atoms in an alkoxy group can be 1 to 30, more specifically 1 to 20.

[0041] In this specification, cycloalkyl groups can be monocyclic or polycyclic rings having 3 to 60 carbon atoms, and specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc. Specifically, the number of carbon atoms in a cycloalkyl group can be 3 to 30, more specifically 3 to 20.

[0042] In this specification, a heterocyclic alkyl group contains at least one non-carbon atom, i.e., a heteroatom. Specifically, it can be a cycloalkyl group containing at least one heteroatom selected from O, N, S, and Se, and can be a monocyclic or polycyclic alkyl group having 2 to 60 carbon atoms. Specifically, the number of carbon atoms in the heterocyclic alkyl group can be 2 to 30, more specifically 2 to 20.

[0043] In this specification, the thioether group contains sulfur (S) and may have 1 to 60 carbon atoms. Specific examples include, but are not limited to, alkyl thioether groups (e.g., dimethyl sulfide), aryl thioether groups (e.g., diphenyl sulfide), and heteroaryl thioether groups substituted with heteroaryl groups. Specifically, the number of carbon atoms in the thioether group may be 1 to 30, and more specifically 1 to 20.

[0044] In this specification, an aryloxy group contains an oxygen atom and may be a substituent directly attached to the oxygen atom. The number of carbon atoms in this group is 6 to 60. Specific examples include, but are not limited to, aryl-substituted oxy groups, such as phenoxy, naphthoxy, and biphenyloxy. A heteroaryloxy group is an oxy group substituted with a heteroaryl group and may have 2 to 60 carbon atoms. Specifically, the number of carbon atoms in an aryloxy group may be 6 to 30, and more specifically 6 to 20.

[0045] In this specification, the sulfo group contains sulfur (S) and may have 1 to 60 carbon atoms. Specific examples include, but are not limited to, alkylthio groups such as methylthio, ethylthio, butylthio, pentylthio, and hexylthio, arylthio groups such as phenylthio and naphthio, and heteroarylthio groups substituted with heteroaryl groups. Specifically, the number of carbon atoms in the sulfo group may be 1 to 30, more specifically 1 to 20.

[0046] In this specification, the silicon group can be a Si-containing substituent directly attached to a Si atom in the form of a free radical, with the number of carbon atoms ranging from 1 to 60. Specific examples include alkylsilyl groups, such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, and propyldimethylsilyl; arylsilyl groups, such as triphenylsilyl, diphenylsilyl, and phenylsilyl; and heteroarylsilyl groups substituted with heteroaryl groups, but are not limited thereto. Specifically, the number of carbon atoms in the silicon group can be from 1 to 30, more specifically from 1 to 20.

[0047] In this specification, the phosphine oxide group contains P=O and may have 1 to 60 carbon atoms. Specific examples include, but are not limited to, alkyl phosphine oxide groups, such as dimethyl phosphine oxide, aryl phosphine oxide groups, such as diphenyl phosphine oxide and dinaphthyl phosphine oxide, and heteroaryl phosphine oxide groups substituted with heteroaryl groups. Specifically, the number of carbon atoms in the phosphine oxide group may be 1 to 30, more specifically 1 to 20.

[0048] In this specification, the aryl group can be monocyclic or polycyclic and has 6 to 60 carbon atoms. Specific examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, etc. Specific examples of polycyclic aryl groups include, but are not limited to, naphthyl, anthraceneyl, phenanthrene, phenylenetriene, pyrene, fluorene, etc. Specifically, the aryl group can have 6 to 50 carbon atoms, more specifically, 6 to 30 carbon atoms.

[0049] In this specification, a heteroaryl group contains at least one non-carbon atom, i.e., a heteroatom. Specifically, it may contain at least one heteroatom selected from O, N, S, and Se, and may be a monocyclic or polycyclic group having 2 to 60 carbon atoms. Specific examples include thiophene, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, triazolyl, acridinel, pyridazinyl, quinolinyl, quinazolinyl, quinoxolinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyridoindolyl, benzothiophene-pyrimidinyl, indoxacarbazolyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzoimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophene, dibenzothiophene, benzofuranyl, phenanthridine, phenanthrolinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, and dibenzofuranyl, but are not limited to these. Specifically, heteroaryl groups can have 2 to 50 carbon atoms, more specifically, 2 to 30 carbon atoms.

[0050] In this specification, the amino group may be selected from the group consisting of -NH2, alkylamino, N-alkylarylamino, arylamino, N-arylheteroarylamino, N-alkylheteroarylamino and heteroarylamino.

[0051] In this specification, arylene refers to a divalent aryl group having two bonding positions with an aryl group, and heteroarylene refers to a divalent heteroaryl group having two bonding positions with a heteroaryl group. The above descriptions of aryl and heteroaryl groups apply to these groups, but each of them is a divalent group.

[0052] In this specification, fused ring groups include fused ring groups fused with an aryl group and a cycloalkyl group, fused ring groups fused with a heteroaryl group and a cycloalkyl group, fused ring groups fused with an aryl group and a heterocycloalkyl group, or fused ring groups fused with a heteroaryl group and a heterocycloalkyl group. According to one embodiment, the tetrahydronaphthyl group shown in the following structural formula may correspond to one of the fused ring groups fused with an aryl group and a cycloalkyl group, and benzo-1,4-dioxane may correspond to one of the fused ring groups fused with an aryl group and a heterocycloalkyl group.

[0053]

[0054] In the chemical formulas or structural formulas in this specification or Indicates the bonding location.

[0055] In the chemical formulas or structural formulas in this specification, the same symbols may be the same or different.

[0056] In this specification, when describing ranges such as "C2 to C50" or "0 to 7," even without special instructions, these ranges can be reduced to various ranges within the stated range and are considered as described in this specification. For example, C2 to C50 can be considered as a combined description of various reduced ranges such as C2 to C50, C5 to C50, C6 to C30, C6 to C20, C6 to C15, C6 to C10, and C12 to C30. Therefore, the descriptions of numerical ranges in this specification may be reduced or corrected in the future.

[0057] In this specification, the term "interaction with dopant" can refer to the coordination of an organic compound with a dopant (e.g., an alkali metal, alkaline earth metal, rare earth metal, or lanthanum metal) within an N-type charge generation layer, and in one embodiment, it can include the case where the organic compound and the dopant combine to form an interstitial state.

[0058] Furthermore, unless otherwise expressly stated, the various embodiments of the present invention can be combined with any other embodiments. The embodiments of the present invention and their effects will be described below.

[0059] In this specification, "organic light-emitting element" can refer to both the organic light-emitting element and the panel containing the organic light-emitting element, or it can refer to an electronic device containing the panel and circuitry. Here, electronic devices may include, for example, display devices, lighting devices, solar cells, portable or mobile terminals (e.g., smartphones, tablets, PDAs, electronic dictionaries, PMPs, etc.), navigation terminals, game consoles, various televisions, various computer monitors, etc., but are not limited to these; they can be any type of device as long as it contains the aforementioned components.

[0060] The present invention will now be described in detail.

[0061] This invention relates to a novel compound and an organic light-emitting element comprising the compound.

[0062] A novel compound according to an embodiment of the present invention can be represented by the following chemical formula 1.

[0063] <Chemical Formula 1>

[0064]

[0065] In the chemical formula 1,

[0066] Ring A is phenyl or naphthyl.

[0067] R1 can be, independently, hydrogen, deuterium, halogen, cyano, nitro, nitrile, hydroxyl, thiol, substituted or unsubstituted C0–C50 amino, substituted or unsubstituted C1–C50 alkyl, substituted or unsubstituted C1–C50 alkenyl, substituted or unsubstituted C1–C50 alkoxy, substituted or unsubstituted C1–C50 thioether, substituted or unsubstituted C0–C50 silyl, substituted or unsubstituted C3–C50 cycloalkyl, substituted or unsubstituted... The following groups may be substituted C2-C50 heterocyclic alkyl groups, substituted or unsubstituted C3-C50 cycloalkenyl groups, substituted or unsubstituted C1-C30 phosphinoalkyl groups, substituted or unsubstituted C2-C50 heterocyclic alkenyl groups, substituted or unsubstituted C6-C50 aryl groups, substituted or unsubstituted C6-C50 aryloxy groups, substituted or unsubstituted C2-C50 heteroaryloxy groups, or substituted or unsubstituted C2-C50 heteroaryl groups, wherein adjacent groups may or may not combine to form a substituted or unsubstituted ring.

[0068] L can be a direct bond, a substituted or unsubstituted C6-C50 arylene, or a substituted or unsubstituted C2-C50 heteroarylene.

[0069] R2 through R5 are each independently hydrogen or deuterium, or adjacent groups may or may not combine to form a ring substituted or unsubstituted with one or more deuterium atoms.

[0070] a is an integer from 0 to 7.

[0071] b is an integer from 0 to 3.

[0072] c is an integer from 0 to 6.

[0073] d and e are each independent integers from 0 to 4.

[0074] f is an integer from 0 to 5.

[0075] One embodiment of the present invention comprises a compound of 1,10-phenanthroline and fluorene, more specifically, 1,10-phenanthroline is bonded to the phenyl or naphthyl group at the metaposition of diphenylfluorene or naphthylphenylfluorene, characterized in that the bond is located at the N position (position 2 or 9) immediately adjacent to 1,10-phenanthroline, and its main structural feature is that there are no other substituents on the fluorene except for hydrogen or deuterium.

[0076] Furthermore, in chemical formula 1 and the following chemical formulas, unless otherwise specifically defined, the substituents for substitution are deuterium, halogen, amino, cyano, hydroxyl, thiol, nitro, nitroso, aminosulfonyl, isothiocyanate, thiocyanate, carboxyl, carbonyl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkylsulfinyl, substituted or unsubstituted C1-C30 alkylsulfonyl, substituted or unsubstituted C1-C30 alkylthioalkyl, substituted or unsubstituted C1-C30 fluoroalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted One or more of the following: C0-C30 amino groups, substituted or unsubstituted C1-C12 N-alkylamino groups, substituted or unsubstituted C2-C20 N,N-dialkylamino groups, substituted or unsubstituted C1-C30 sulfide groups, substituted or unsubstituted C1-C6 N-alkylaminosulfonyl groups, substituted or unsubstituted C2-C12 N,N-dialkylaminosulfonyl groups, substituted or unsubstituted C0-C30 silyl groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C1-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C50 aryl groups, and substituted or unsubstituted C3-C50 heteroaryl groups. More specifically, the substituent may be at least one of deuterium atom, halogen group, cyano group, C1-C10 alkyl group, C1-C10 alkoxy group, C1-C10 alkylthio group, C1-C10 fluoroalkyl group with hydrogen substituted by fluorine, substituted or unsubstituted C6-C20 aryl group, and substituted or unsubstituted C3-C20 heteroaryl group. In one embodiment, examples may include deuterium atom, halogen group, cyano group, methyl group, ethyl group, tert-butyl group, -CD3 group, phenyl group, naphthyl group, biphenyl group, pyridyl group, etc.

[0077] Specifically, according to one embodiment, chemical formula 1 can be one of the following chemical formulas 2 to 4. Chemical formula 2 represents the case where ring A is phenyl, and chemical formulas 3 and 4 represent the case where ring A is naphthyl.

[0078] <Chemical Formula 2>

[0079]

[0080] <Chemical Formula 3>

[0081]

[0082] <Chemical Formula 4>

[0083]

[0084] In chemical formulas 2 to 4, the definitions of R1, L, R2 to R5, and a to f are the same as those in chemical formula 1.

[0085] Specifically, the chemical formula 2 can be one of the following chemical formulas 2-1 to 2-3. Chemical formula 2-1 represents the case of ortho- or 1,2-phenylene bonding, chemical formula 2-2 represents the case of meta- or 1,3-phenylene bonding, and chemical formula 2-3 represents the case of para- or 1,4-phenylene bonding.

[0086] <Chemical Formula 2-1>

[0087]

[0088] <Chemical Formula 2-2>

[0089]

[0090] <Chemical Formula 2-3>

[0091]

[0092] In chemical formulas 2-1 to 2-3, the definitions of R1, L, R2 to R5, and a to f are the same as in chemical formula 1.

[0093] Specifically, chemical formula 3 can be one of the following chemical formulas 3-1 to 3-3. Chemical formula 3-1 represents the case of 2,6-naphthyl bonding, chemical formula 3-2 represents the case of 2,7-naphthyl bonding, and chemical formula 3-3 represents the case of 1,3-naphthyl bonding.

[0094] <Chemical Formula 3-1>

[0095]

[0096] <Chemical Formula 3-2>

[0097]

[0098] <Chemical Formula 3-3>

[0099]

[0100] In the chemical formulas 3-1 to 3-3, the definitions of R1, L, R2 to R5, and a to f are the same as in chemical formula 1.

[0101] Specifically, chemical formula 4 can be either chemical formula 4-1 or 4-2 as shown below. Chemical formula 4-1 indicates the case of bonding via 1,4-naphthyl groups, and chemical formula 4-2 indicates the case of bonding via 1,3-naphthyl groups.

[0102] <Chemical Formula 4-1>

[0103]

[0104] <Chemical Formula 4-2>

[0105]

[0106] In chemical formulas 4-1 and 4-2, R1, L, R2 to R5, and a to f are defined as in chemical formula 1.

[0107] Meanwhile, in the chemical formula,

[0108] According to one embodiment of the present invention, R1 can be independently one of hydrogen, deuterium, methyl, -CD3, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and naphthidyl, specifically hydrogen, phenyl, or pyridyl, and more specifically hydrogen or phenyl.

[0109] According to one embodiment of the present invention, a can be an integer from 0 to 3, specifically an integer from 0 to 2, more specifically 0 or 1.

[0110] Furthermore, according to one embodiment of the invention, adjacent groups of R1 can combine to form a ring substituted or unsubstituted by one or more substituents, specifically a substituted or unsubstituted benzene ring. In this case, the 1,10-phenanthroline moiety in Formula 1 can be specifically represented by one of the following structural formulas P-1 to P-4.

[0111] <Structural Formula P-1>

[0112]

[0113] <Structural Formula P-2>

[0114]

[0115] <Structural Formula P-3>

[0116]

[0117] <Structural Formula P-4>

[0118]

[0119] In the structural formulas P-1 to P-4, R6 has the same definition as R1 in chemical formula 1.

[0120] g can be an integer from 0 to 9,

[0121] This indicates the position in chemical formula 1 where L is bonded.

[0122] Specifically, similar to R1, R6 can be one of hydrogen, deuterium, methyl, -CD3, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and naphthidyl, specifically, it can be hydrogen, phenyl, or pyridyl, and more specifically, it can be hydrogen or phenyl.

[0123] The g can be an integer from 0 to 3, specifically an integer from 0 to 2, and more specifically 0 or 1.

[0124] Furthermore, the bonding position of R1 is preferably adjacent to the N atom of 1,10-phenanthroline, as shown in Chemical Formula 5 below. In other words, when fluorene is bonded to the N atom immediately adjacent to position 1 in 1,10-phenanthroline, R1 can be bonded to position 9, immediately adjacent to position 10 of the N atom. Based on this, according to one embodiment, Chemical Formula 1 can be represented as Chemical Formula 5 below. This also applies to R6, and R6 in structural formulas P-1 to P-4 can also be bonded to the N atom immediately adjacent to it.

[0125] <Chemical Formula 5>

[0126]

[0127] In Formula 5, L, R2 to R5, and b to f are defined as in Formula 1, and R1 is defined as in Formula 1. Specifically, it can be hydrogen, phenyl, or pyridyl, and more specifically, it can be hydrogen or phenyl. When R1 is phenyl, it may be preferred in terms of structural and thermal stability, and may also be preferred in terms of increasing π-conjugation and improving electron mobility. This can effectively reduce the operating voltage of the device and extend its lifespan.

[0128] Meanwhile, according to one embodiment of the present invention, L can be independently a direct bond, a substituted or unsubstituted C6-C20 arylene, or a substituted or unsubstituted C2-C20 heteroarylene. More specifically, direct bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted phenanthylene, substituted or unsubstituted anthraceneylene, substituted or unsubstituted trepenylene, substituted or unsubstituted benzophenanthylene, substituted or unsubstituted benzoanthraceneylene, substituted or unsubstituted pyreneylene, substituted or unsubstituted diphenylfluoreneylene, substituted or unsubstituted dimethylfluoreneylene, substituted or unsubstituted spirodifluoreneylene, substituted or unsubstituted pyridylene, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted triazinylene, substituted or unsubstituted quinolinylene, etc. The derivatives can be substituted or unsubstituted isoquinoline, substituted or unsubstituted quinoazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted phthalazinyl, substituted or unsubstituted terpinenyl, substituted or unsubstituted 1,5-naphthidyl, substituted or unsubstituted 1,6-naphthidyl, substituted or unsubstituted 1,7-naphthidyl, substituted or unsubstituted 1,8-naphthidyl, substituted or unsubstituted 2,5-naphthidyl, substituted or unsubstituted 2,6-naphthidyl, substituted or unsubstituted 2,7-naphthidyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzothiazolyl, or substituted or unsubstituted benzimidazolyl. According to one embodiment of the invention, when b is 2 or greater, the plurality of Ls can be the same or different. Specifically, b can be 0, 1, or 2. According to one embodiment of the present invention, L can be independently one of the following structural formulas, but is not particularly limited thereto. For the left-right asymmetrical structures in the following structural formulas, the left and right sides are not limited to the figures below, and can be changed to all possible cases.

[0129]

[0130]

[0131]

[0132] Furthermore, according to one embodiment of the present invention, R2 to R5 can each be independently hydrogen or deuterium, specifically, all of them can be hydrogen. In this way, by avoiding the introduction of additional functional groups onto fluorene and placing fluorene at the end, the fill density and refractive index can be increased, thereby extending the device lifetime.

[0133] Furthermore, according to one embodiment of the present invention, one or more groups among R3, R4, and R5 can bond to each other to form a ring substituted or unsubstituted with one or more deuterium atoms; specifically, a benzene ring substituted or unsubstituted with one or more deuterium atoms can be formed. In this case, the fluorene portion in the chemical formula 1 can be specifically represented by one of the following structural formulas F-1 to F-5.

[0134] <Structural Formula F-1>

[0135]

[0136] <Structural Formula F-2>

[0137]

[0138] <Structural Formula F-3>

[0139]

[0140] <Structural Formula F-4>

[0141]

[0142] <Structural Formula F-5>

[0143]

[0144] In the structural formulas F-1 to F-5, ring A is defined as shown in chemical formula 1.

[0145] R2 to R5 and R7 are each independently either hydrogen or deuterium.

[0146] The definitions of c to f are shown in Chemical Formula 1.

[0147] h is an independent integer from 0 to 6.

[0148] This indicates the bonding position between it and the linking group L in chemical formula 1.

[0149] Specifically, R2 through R5 and R7 can all be hydrogen.

[0150] In summary, according to an embodiment of the present invention, chemical formula 1 can be one of the following chemical formulas A to H.

[0151] <Chemical Formula A>

[0152]

[0153] <Chemical Formula B> <Chemical Formula C>

[0154]

[0155] <Chemical Formula D> <Chemical Formula E>

[0156]

[0157] <Chemical Formula F> <Chemical Formula G> <Chemical Formula H>

[0158]

[0159] In the chemical formulas A to H, the definitions of R1, L and b are the same as in chemical formula 1.

[0160] According to one embodiment of the invention, ring A is preferably a naphthyl group, or at least one of the adjacent groups from R3 to R5 is bonded to each other to form a ring. In other words, the fluorene substituent preferably comprises a naphthyl group with two fused benzene rings, as shown in the chemical formulas B to H. This structure enhances conjugation, thereby enhancing molecular stability, improving electron mobility, and ensuring that the RE value is below a certain level, ultimately improving device performance, such as high efficiency and long lifetime. More specifically, the naphthyl group may be positioned above the fluorene group, as shown in chemical formulas B to E; more specifically, as shown in chemical formulas B and C.

[0161] According to one embodiment of the present invention, the compound represented by chemical formula 1 may be selected from compounds 1 to 543 described below. The following compounds are for illustrative purposes only and the invention is not limited thereto.

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187] The novel compounds of the present invention described above are particularly suitable for the host of N-type charge-generating layers because, by introducing 1,10-phenanthroline with non-shared electron pairs, they can be easily combined with dopants such as lithium and ytterbium, and also have excellent thermal stability by introducing rigid fluorene substituents.

[0188] Furthermore, due to its inverse structure, where 1,10-phenanthroline is bonded to a phenyl or naphthyl group above diphenylfluorene or naphthylphenylfluorene, it has a lower RE (recombination energy) value compared to the structure with fluorene bonded below, which can improve the efficiency of the device.

[0189] Furthermore, due to the N-position bonding immediately adjacent to 1,10-phenanthroline, the structure expands the conjugation, thereby reducing the RE value compared to other positions and ultimately improving the efficiency of the element.

[0190] Furthermore, since fluorene is not replaced by any functional groups other than hydrogen and deuterium, positioning fluorene at the very end can increase the fill density and refractive index, thereby extending the lifespan of the device.

[0191] The novel compounds of this invention can be effectively applied to one or more organic layers in the organic layers of an organic light-emitting element, including the electron transport layer (ETL), hole blocking layer (HBL), and N-type charge generation layer (N-CGL). In particular, when applied to the main body of the N-type charge generation layer of a series organic light-emitting element, it can achieve low voltage, high efficiency, and long lifespan of the element.

[0192] In this specification, the RE value (reorganization energy) is calculated as (electron extraction potential, EEP) - (electron affinity, EA), where EEP represents the energy required for the anionic structure to transform into a cation, and EA represents the energy of the anion in the ground state (neutral) structure. Reducing the RE value below a certain level may improve component performance, such as current efficiency.

[0193] The novel compounds of this invention can be effectively applied to one or more organic layers in the organic layers of organic light-emitting elements, including the electron transport layer (ETL), hole blocking layer (HBL), and N-type charge generation layer (N-CGL). In particular, when applied to the N-type charge generation layer of a series organic light-emitting element, it can achieve low voltage, high efficiency, and long lifetime of the element.

[0194] The novel compounds of this invention relate to a novel compound suitable for charge generation layers (CGLs) in series devices, particularly N-type charge generation layers (nCGLs), which can improve device efficiency, reduce operating voltage, and extend device lifetime. Furthermore, the invention is not limited to this, and can also be applied to organic layers requiring compounds with excellent electron mobility, such as electron transport layers (ETLs) and hole blocking layers (HBLs).

[0195] The present invention may include an organic light-emitting element comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein the at least one organic layer comprises a compound according to Chemical Formula 1. Specifically, the organic layer comprising the compound may be an electron transport layer (ETL), a hole blocking layer (HBL), or a charge generating layer (CGL).

[0196] Furthermore, the present invention may include a tandem organic light-emitting element, the element comprising a first electrode and a second electrode, a plurality of light-emitting portions located between the first electrode and the second electrode, and at least one charge-generating layer located between two adjacent light-emitting portions, wherein the at least one charge-generating layer is an N-type charge-generating layer comprising a compound represented by chemical formula 1.

[0197] The organic light-emitting elements and tandem organic light-emitting elements according to the present invention will be described in more detail below.

[0198] The organic light-emitting element has an organic layer located between a first electrode and a second electrode. The organic layer may be configured to include one or more organic layers, specifically, it may be configured to include one or more known organic layers selected from those constituting the light-emitting portion, such as a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL).

[0199] The hole injection layer (HIL) is a layer in which holes are injected from the electrode. As a hole injection material, a compound with hole transport capability is preferred. This compound has excellent hole injection effect on the anode, excellent hole injection effect on the light-emitting layer or light-emitting material, can prevent excitons generated in the light-emitting layer from moving to the electron injection layer or electron injection material, and also has excellent thin film formation capability.

[0200] The hole transport layer (HTL) is the layer that receives holes from the hole injection layer and transports them to the light-emitting layer. The hole transport material is preferably a material with high hole mobility because it can effectively transport holes from the anode or hole injection layer to the light-emitting layer.

[0201] An emitter layer (EML) is a layer that emits light through the recombination of electrons and holes. Luminescent materials are those capable of emitting visible light by transporting and recombinating holes and electrons from hole transport layers and electron transport layers; materials with high fluorescence or phosphorescence quantum efficiencies are preferred. Specifically, an emitter layer may include a host material and dopants.

[0202] The electron transport layer (ETL) is the layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. Electron transport materials are materials that can easily receive electrons from the cathode and transport them to the light-emitting layer, preferably materials with high electron mobility.

[0203] An electron injection layer (EIL) is a layer that injects electrons from an electrode. Preferably, it is a compound that has the ability to transport electrons, the effect of injecting electrons from the cathode, excellent electron injection effect on the light-emitting layer or light-emitting material, the ability to prevent excitons generated in the light-emitting layer from moving to the hole injection layer, and also has excellent thin film forming ability.

[0204] Additionally, the organic layer can also include a hole-blocking layer (HBL). The HBL can be located between the light-emitting layer and the electron transport layer to reduce the problem of hole intrusion into the electron transport layer (ETL) in the HIL. The HBL is also one of the electron transport layers, and materials capable of transporting electrons are suitable.

[0205] In the organic layer of such organic light-emitting elements, the novel compound of chemical formula 1 according to the present invention is a material with excellent electron transport capability, and is therefore preferably applied to the electron transport layer or hole blocking layer in the electron transport region.

[0206] Meanwhile, the structure of the organic light-emitting element can be modified or altered in various ways. According to one embodiment, it can be a tandem organic light-emitting element, wherein two or more light-emitting portions (or light-emitting units) containing light-emitting layers are stacked between a first electrode and a second electrode. In this tandem structure, in addition to the aforementioned organic layers, a charge-generating layer (CGL) for controlling charge balance can also be included as one of the organic layers, and can be located at one or more positions between two adjacent light-emitting portions. The charge-generating layer can be composed of multiple layers, including an N-type charge-generating layer for injecting electrons and a P-type charge-generating layer for injecting holes, but is not limited to this; it can also be composed of a single layer.

[0207] The novel compounds of this invention can also be applied to the charge generation layer of such tandem organic light-emitting elements, specifically to N-type charge generation layers. The N-type charge generation layer can be composed of an organic material layer doped with dopants such as metals, specifically configured to include a host and a dopant. In this case, the novel compounds of this invention can be used as the host, and by including 1,10-phenanthroline with lone pairs of electrons, the compounds of this invention can interact smoothly with the dopant.

[0208] Meanwhile, the dopant can be a material containing a metallic element, specifically one or more of a metal, a metal compound, or a metal-organic complex. The metallic element can be at least one selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), ytterbium (Yb), samarium (Sm), tin (Sn), copper (Cu), titanium (Ti), cadmium (Cd), mercury (Hg), lead (Pb), bismuth (Bi), zinc (Zn), iron (Fe), cobalt (Co), nickel (Ni), indium (In), gallium (Ga), thorium (Th), uranium (U), silver (Ag), aluminum (Al), gold (Au), molybdenum (Mo), niobium (Nb), palladium (Pd), platinum (Pt), and europium (Eu), and according to one embodiment, it can be lithium or ytterbium. The proportion of these dopants can be 0.1 to 20% by weight relative to the entire host material, specifically 0.5 to 15% by weight, but is not limited thereto and can vary depending on the type of metal element.

[0209] The present invention will be described in more detail below with reference to synthetic examples, experimental examples and embodiments, but the following content does not limit the scope of the present invention.

[0210] Synthesis Examples: Compound Synthesis

[0211] Synthesis of Intermediate 1

[0212]

[0213] In a round-bottom flask, 9-(3-bromophenyl)-9-phenyl-9H-fluorene (70 g, 176.75 mmol), bis(pinacol)boron (53.86 g, 212.09 mmol), sphos (4.35 g, 10.60 mmol), potassium acetate (34.70 g, 353.49 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (3.88 g, 5.30 mmol) were added and refluxed overnight in 600 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain the filtrate. The filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain the filtrate. The filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to obtain intermediate 1 (64.8 g, 82.53%).

[0214] Synthesis Example 1: Synthesis of Compound 4

[0215]

[0216] Intermediate 1 (10 g, 22.50 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (9.05 g, 27.00 mmol), potassium carbonate (6.22 g, 45.01 mmol), and tetra(triphenylphosphine)palladium (0.78 g, 0.68 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 4 (9.4 g, 72.94%).

[0217] Synthesis of intermediate 2

[0218]

[0219] In a round-bottom flask, 9-(2-bromophenyl)-9-phenyl-9H-fluorene (15 g, 37.87 mmol), bis(pinacol)boron (11.54 g, 45.45 mmol), sphos (0.93 g, 2.27 mmol), potassium acetate (7.43 g, 75.75 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.93 g, 2.27 mmol) were added and refluxed in 150 mL of 1,4-dioxane with stirring overnight. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered through silica gel and diatomaceous earth under reduced pressure, and concentrated under reduced pressure to give intermediate 2 (12.5 g, 74.29%).

[0220] Synthesis Example 2: Synthesis of Compound 5

[0221]

[0222] Intermediate 2 (12.5 g, 26.11 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (10.50 g, 31.34 mmol), potassium carbonate (7.22 g, 52.23 mmol), and tetra(triphenylphosphine)palladium (0.91 g, 0.78 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 5 (11.4 g, 76.23%).

[0223] Synthesis of intermediate 3

[0224]

[0225] In a round-bottom flask, 9-(4-bromophenyl)-9-phenyl-9H-fluorene (30 g, 75.51 mmol), bis(pinacol)boron (23.01 g, 90.61 mmol), sphos (1.86 g, 4.53 mmol), potassium acetate (14.82 g, 151.01 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (1.66 g, 2.27 mmol) were added and refluxed overnight in 300 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The obtained filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to give intermediate 3 (31.2 g, 92.72%).

[0226] Synthesis Example 3: Synthesis of Compound 6

[0227]

[0228] Intermediate 3 (10 g, 22.50 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (9.05 g, 27.00 mmol), potassium carbonate (6.22 g, 45.01 mmol), and tetra(triphenylphosphine)palladium (0.78 g, 0.68 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 6 (9.4 g, 72.91%).

[0229] Synthesis Example 4: Synthesis of Compound 7

[0230]

[0231] Intermediate 1 (10 g, 22.50 mmol), 2-(3-bromophenyl)-1,10-phenanthroline (9.05 g, 27.00 mmol), potassium carbonate (6.22 g, 45.01 mmol), and tetra(triphenylphosphine)palladium (0.78 g, 0.68 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 7 (8.9 g, 69.03%).

[0232] Synthesis Example 5: Synthesis of Compound 10

[0233]

[0234] Intermediate 1 (10 g, 22.50 mmol), 2-(4-bromonaphth-1-yl)-1,10-phenanthroline (10.40 g, 27.00 mmol), potassium carbonate (6.22 g, 45.01 mmol), and tetra(triphenylphosphine)palladium (0.78 g, 0.68 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 10 (11.6 g, 82.74%).

[0235] Synthesis Example 6: Synthesis of Compound 13

[0236]

[0237] Intermediate 1 (10 g, 22.50 mmol), 2-(6-bromonaphth-2-yl)-1,10-phenanthroline (10.40 g, 27.00 mmol), potassium carbonate (6.22 g, 45.01 mmol), and tetra(triphenylphosphine)palladium (0.78 g, 0.68 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 13 (10.2 g, 72.76%).

[0238] Synthesis of intermediate 4

[0239]

[0240] Intermediate 3 (15 g, 33.75 mmol), 1-(6-bromopyridin-2-yl)ethyl-1-one (8.10 g, 40.51 mmol), potassium carbonate (9.33 g, 67.51 mmol), and tetrakis(triphenylphosphine)palladium (1.17 g, 1.01 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The filtrate was purified by column chromatography to obtain intermediate 4 (10.4 g, 70.39%).

[0241] Synthesis Example 7: Synthesis of Compound 18

[0242]

[0243] 8-Aminoquinoline-7-carboxaldehyde (4.91 g, 28.52 mmol), intermediate 4 (10.4 g, 23.77 mmol), and 70 mL of toluene were added to a round-bottom flask. Potassium hydroxide (2.56 g, 45.71 mmol) dissolved in 50 mL of ethanol was added dropwise, and the mixture was refluxed and stirred overnight. After the reaction was complete, the mixture was cooled to room temperature, methanol was added, and the mixture was filtered. The solid was washed with methanol. The solid dissolved in toluene, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, and recrystallized from toluene to give compound 18 (8.5 g, 62.33%).

[0244] Synthesis of intermediate 5

[0245]

[0246] 9-(3-bromophenyl)-9-phenyl-9H-fluorene (15 g, 37.87 mmol), 2-(4-chlorophenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborane (9.92 g, 41.66 mmol), potassium carbonate (10.47 g, 75.75 mmol), and tetra(triphenylphosphine)palladium (1.32 g, 1.14 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature and concentrated under reduced pressure to obtain a filtrate. The filtrate was extracted with ethyl acetate and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain a filtrate. The filtrate was purified by column chromatography to give intermediate 5 (12.6 g, 77.56%).

[0247] Synthesis of intermediate 6

[0248]

[0249] 9-(4'-chloro-[1,1'-biphenyl]-3-yl)-9-phenyl-9H-fluorene (12.6 g, 29.37 mmol), bis(pinacol)boron (8.95 g, 35.25 mmol), sphos (0.72 g, 1.76 mmol), potassium acetate (5.77 g, 58.75 mmol), and [1,1'-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.64 g, 0.88 mmol) were added to a round-bottom flask and refluxed in 150 mL of 1,4-dioxane with stirring overnight. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain the filtrate. The filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to obtain intermediate 6 (12.8 g, 83.72%).

[0250] Synthesis Example 8: Synthesis of Compound 22

[0251]

[0252] Intermediate 6 (12.8 g, 24.59 mmol), 2-(4-bromonaphth-1-yl)-1,10-phenanthroline (10.42 g, 27.05 mmol), potassium carbonate (6.80 g, 49.19 mmol), and tetra(triphenylphosphine)palladium (0.85 g, 0.74 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 22 (11.8 g, 68.66%).

[0253] Synthesis of intermediate 7

[0254]

[0255] In a round-bottom flask, 9-(7-bromonaphth-2-yl)-9-phenyl-9H-fluorene (40 g, 89.41 mmol), bis(pinacol)boron (27.25 g, 107.29 mmol), sphos (2.20 g, 5.36 mmol), potassium acetate (17.55 g, 178.82 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (1.96 g, 2.68 mmol) were added. The mixture was refluxed and stirred overnight in 300 mL of 1,4-dioxane. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain the filtrate. The filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to obtain intermediate 7 (41.2 g, 93.20%).

[0256] Synthesis Example 9: Synthesis of Compound 28

[0257]

[0258] Intermediate 7 (10 g, 20.22 mmol), 2-bromo-1,10-phenanthroline (5.76 g, 22.25 mmol), potassium carbonate (5.60 g, 40.45 mmol), and tetrakis(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 28 (8.5 g, 76.88%).

[0259] Synthesis of intermediate 8

[0260]

[0261] In a round-bottom flask, 9-(6-bromonaphth-2-yl)-9-phenyl-9H-fluorene (30 g, 67.06 mmol), bis(pinacol)boron (20.43 g, 80.47 mmol), sphos (1.65 g, 4.02 mmol), potassium acetate (13.16 g, 134.11 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (1.47 g, 2.01 mmol) were added. The mixture was refluxed overnight in 300 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain the filtrate. The filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to obtain intermediate 8 (30.9 g, 93.2%).

[0262] Synthesis Example 10: Synthesis of Compound 29

[0263]

[0264] Intermediate 8 (10 g, 20.22 mmol), 2-bromo-1,10-phenanthroline (5.76 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetrakis(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 29 (7.9 g, 71.45%).

[0265] Synthesis of intermediate 9

[0266]

[0267] In a round-bottom flask, 9-(4-bromonaphth-1-yl)-9-phenyl-9H-fluorene (15 g, 33.53 mmol), bis(pinacol)boron (10.22 g, 40.23 mmol), sphos (0.83 g, 2.01 mmol), potassium acetate (6.58 g, 67.06 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.74 g, 1.01 mmol) were added. The mixture was refluxed overnight in 300 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure. The resulting filtrate was dissolved in dichloromethane, filtered through silica gel and diatomaceous earth under reduced pressure, and concentrated under reduced pressure to give intermediate 9 (12.7 g, 76.61%).

[0268] Synthesis Example 11: Synthesis of Compound 30

[0269]

[0270] Intermediate 9 (12.7 g, 25.69 mmol), 2-bromo-1,10-phenanthroline (7.32 g, 28.25 mmol), potassium carbonate (7.10 g, 51.37 mmol), and tetrakis(triphenylphosphine)palladium (0.89 g, 0.77 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 30 (9.2 g, 65.52%).

[0271] Synthesis Example 12: Synthesis of Compound 32

[0272]

[0273] Intermediate 8 (10 g, 20.22 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 44.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 32 (8.7 g, 69.07%).

[0274] Synthesis Example 13: Synthesis of Compound 34

[0275]

[0276] Intermediate 7 (10 g, 20.22 mmol), 2-(3-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 44.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 34 (9.2 g, 73.04%).

[0277] Synthesis Example 14: Synthesis of Compound 37

[0278]

[0279] Intermediate 7 (10 g, 20.22 mmol), 2-(4-bromonaphth-1-yl)-1,10-phenanthroline (8.57 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 37 (10.3 g, 75.69%).

[0280] Synthesis of Intermediate 10

[0281]

[0282] In a round-bottom flask, 9-(4-bromophenyl)-9-(naphth-2-yl)-9H-fluorene (10 g, 22.35 mmol), bis(pinacol)boron (6.81 g, 26.82 mmol), sphos (0.55 g, 1.34 mmol), potassium acetate (4.39 g, 44.70 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.49 g, 0.67 mmol) were added. The mixture was refluxed overnight in 120 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure. The resulting filtrate was dissolved in dichloromethane, filtered through silica gel and diatomaceous earth under reduced pressure, and concentrated under reduced pressure to give intermediate 10 (9.8 g, 88.67%).

[0283] Synthesis Example 15: Synthesis of Compound 66

[0284]

[0285] Intermediate 10 (9.8 g, 19.82 mmol), 2-bromo-1,10-phenanthroline (5.65 g, 21.80 mmol), potassium carbonate (5.47 g, 39.64 mmol), and tetrakis(triphenylphosphine)palladium (0.69 g, 0.59 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 66 (8.6 g, 79.37%).

[0286] Synthesis of intermediate 11

[0287]

[0288] In a round-bottom flask, 9-(4-bromophenyl)-9-(naphth-1-yl)-9H-fluorene (10 g, 22.35 mmol), bis(pinacol)boron (6.81 g, 26.82 mmol), sphos (0.55 g, 1.34 mmol), potassium acetate (4.39 g, 44.70 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.49 g, 0.67 mmol) were added. The mixture was refluxed and stirred overnight in 120 mL of 1,4-dioxane. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain the filtrate. The filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to obtain intermediate 11 (9.7 g, 87.77%).

[0289] Synthesis Example 16: Synthesis of Compound 70

[0290]

[0291] Intermediate 11 (9.7 g, 19.62 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (7.23 g, 21.58 mmol), potassium carbonate (5.42 g, 39.24 mmol), and tetra(triphenylphosphine)palladium (0.68 g, 0.59 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 70 (9.1 g, 74.48%).

[0292] Synthesis of intermediate 12

[0293]

[0294] In a round-bottom flask, 9-(3-bromophenyl)-9-(naphth-2-yl)-9H-fluorene (35 g, 78.23 mmol), bis(pinacol)boron (23.84 g, 93.88 mmol), sphos (1.92 g, 4.69 mmol), potassium acetate (15.35 g, 156.47 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (1.71 g, 2.35 mmol) were added. The mixture was refluxed overnight in 300 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain the filtrate. The filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to obtain intermediate 12 (32.4 g, 83.76%).

[0295] Synthesis Example 17: Synthesis of Compound 71

[0296]

[0297] Intermediate 12 (10 g, 20.22 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 71 (8.8 g, 69.87%).

[0298] Synthesis of intermediate 13

[0299]

[0300] In a round-bottom flask, 7-(3-bromophenyl)-7-phenyl-7H-benzo[c]fluorene (35 g, 78.23 mmol), bis(pinacol)boron (23.84 g, 93.88 mmol), sphos (1.92 g, 4.69 mmol), potassium acetate (15.35 g, 156.47 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (1.71 g, 2.35 mmol) were added. The mixture was refluxed overnight in 300 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure. The resulting filtrate was dissolved in dichloromethane, filtered through silica gel and diatomaceous earth under reduced pressure, and concentrated under reduced pressure to give intermediate 13 (31.0 g, 80.14%).

[0301] Synthesis Example 18: Synthesis of Compound 72

[0302]

[0303] Intermediate 13 (10 g, 20.22 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 72 (8.6 g, 68.28%).

[0304] Synthesis of intermediate 14

[0305]

[0306] In a round-bottom flask, 11-(3-bromophenyl)-11-phenyl-11H-benzo[b]fluorene (25 g, 55.88 mmol), bis(pinacol)boron (17.03 g, 67.06 mmol), sphos (1.38 g, 3.35 mmol), potassium acetate (10.97 g, 111.76 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (1.23 g, 1.68 mmol) were added. The mixture was refluxed overnight in 300 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure. The filtrate was dissolved in dichloromethane, filtered through silica gel and diatomaceous earth under reduced pressure, and concentrated under reduced pressure to obtain intermediate 14 (21.1 g, 76.37%).

[0307] Synthesis Example 19: Synthesis of Compound 73

[0308]

[0309] Intermediate 14 (10 g, 20.22 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 73 (7.9 g, 62.72%).

[0310] Synthesis of Intermediate 15

[0311]

[0312] 11-(3-bromophenyl)-11-phenyl-11H-benzo[a]fluorene (10 g, 22.35 mmol), bis(pinacol)boron (6.81 g, 26.82 mmol), sphos (0.55 g, 1.34 mmol), potassium acetate (4.39 g, 44.70 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.49 g, 0.67 mmol) were added to a round-bottom flask and refluxed in 300 mL of 1,4-dioxane with stirring overnight. After the reaction was completed, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure to obtain the filtrate. The filtrate was dissolved in dichloromethane, filtered under reduced pressure through silica gel and diatomaceous earth, and concentrated under reduced pressure to obtain intermediate 15 (8.7 g, 78.72%).

[0313] Synthesis Example 20: Synthesis of Compound 74

[0314]

[0315] Intermediate 15 (8.7 g, 17.60 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (6.49 g, 19.36 mmol), potassium carbonate (4.86 g, 35.19 mmol), and tetra(triphenylphosphine)palladium (0.61 g, 0.53 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform and then filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 74 (7.9 g, 72.09%).

[0316] Synthesis of intermediate 16

[0317]

[0318] In a round-bottom flask, 9-(4-bromophenyl)-9-(naphth-1-yl)-9H-fluorene (10 g, 22.35 mmol), bis(pinacol)boron (6.81 g, 26.82 mmol), sphos (0.55 g, 1.34 mmol), potassium acetate (4.39 g, 44.70 mmol), and [1,1′-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.49 g, 0.67 mmol) were added. The mixture was refluxed overnight in 300 mL of 1,4-dioxane. After the reaction was complete, the mixture was cooled to room temperature, concentrated under reduced pressure, and the filtrate was extracted with dichloromethane and water. The organic layer was dried over MgSO4 and concentrated under reduced pressure. The resulting filtrate was dissolved in dichloromethane, filtered through silica gel and diatomaceous earth under reduced pressure, and concentrated under reduced pressure to give intermediate 16 (8.1 g, 73.29%).

[0319] Synthesis Example 21: Synthesis of Compound 80

[0320]

[0321] Intermediate 16 (8.1 g, 16.38 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (6.04 g, 18.02 mmol), potassium carbonate (4.53 g, 32.76 mmol), and tetra(triphenylphosphine)palladium (0.57 g, 0.49 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 80 (8.2 g, 80.37%).

[0322] Synthesis Example 22: Synthesis of Compound 86

[0323]

[0324] Intermediate 12 (10 g, 20.22 mmol), 2-(3-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 86 (8.1 g, 64.31%).

[0325] Synthesis Example 23: Synthesis of Compound 88

[0326]

[0327] Intermediate 14 (10 g, 20.22 mmol), 2-(3-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 88 (9.0 g, 71.45%).

[0328] Synthesis Example 24: Synthesis of Compound 89

[0329]

[0330] Intermediate 13 (10 g, 20.22 mmol), 2-(3-bromophenyl)-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight with 125 mL of 1,4-dioxane and 60 mL of water. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 89 (7.8 g, 61.93%).

[0331] Synthesis Example 25: Synthesis of Compound 101

[0332]

[0333] Intermediate 12 (10 g, 20.22 mmol), 2-(4-bromonaphth-1-yl)-1,10-phenanthroline (8.57 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 101 (9.4 g, 69.13%).

[0334] Synthesis Example 26: Synthesis of Compound 226

[0335]

[0336] Intermediate 3 (10 g, 22.51 mmol), 2-(4-bromophenyl)-9-phenyl-1,10-phenanthroline (10.18 g, 24.76 mmol), potassium carbonate (6.22 g, 45.01 mmol), and tetra(triphenylphosphine)palladium (0.78 g, 0.68 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 226 (9.8 g, 67.1%).

[0337] Synthesis Example 27: Synthesis of Compound 227

[0338]

[0339] Intermediate 1 (10 g, 22.51 mmol), 2-(3-bromophenyl)-1,10-phenanthroline (10.18 g, 24.76 mmol), potassium carbonate (6.22 g, 45.01 mmol), and tetra(triphenylphosphine)palladium (0.78 g, 0.68 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 227 (10.1 g, 69.15%).

[0340] Synthesis Example 28: Synthesis of Compound 230

[0341]

[0342] Intermediate 1 (10 g, 21.68 mmol), 2-(4-bromonaphthyl-1-yl)-9-phenyl-1,10-phenanthroline (9.81 g, 23.84 mmol), potassium carbonate (5.99 g, 43.35 mmol), and tetra(triphenylphosphine)palladium (0.75 g, 0.65 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 230 (9.5 g, 62.71%).

[0343] Synthesis Example 29: Synthesis of Compound 250

[0344]

[0345] Intermediate 8 (10 g, 20.22 mmol), 2-bromo-9-phenyl-1,10-phenanthroline (7.46 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetrakis(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 250 (9.2 g, 73.04%).

[0346] Synthesis Example 30: Synthesis of Compound 252

[0347]

[0348] Intermediate 7 (10 g, 20.22 mmol), 2-(4-bromophenyl)-9-phenyl-1,10-phenanthroline (9.15 g, 22.25 mmol), potassium carbonate (5.59 g, 40.45 mmol), and tetra(triphenylphosphine)palladium (0.70 g, 0.61 mmol) were added to a round-bottom flask and refluxed overnight in 125 mL of 1,4-dioxane and 60 mL of water with stirring. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed with water and ethanol. The solid was dissolved in chloroform, and the filtrate was filtered under reduced pressure through silica gel and diatomaceous earth to obtain the filtrate. The filtrate was concentrated under reduced pressure, dissolved in chloroform, and recrystallized from ethanol to give compound 252 (10.6 g, 74.99%).

[0349] Experimental Example: Fabrication and Evaluation of Tandem Organic Light-Emitting Elements

[0350] Comparative Example 1

[0351] The ITO substrate was patterned to form an anode with a light-emitting area of ​​2mm x 2mm, and then cleaned with isopropanol and ultraviolet ozone, respectively. Afterward, the ITO substrate was mounted on the support of a vacuum deposition apparatus, and pressure was applied to achieve a vacuum level of 1 x 10⁻⁶. -7 Afterwards, a plasma treatment was performed for 3 minutes under an N2 atmosphere. Then, a 5 nm thick HAT-CN compound was vacuum-deposited on the substrate to form the first hole injection layer, and a 20 nm thick NPB material was vacuum-deposited on it to form the first hole transport layer.

[0352] Subsequently, a 20 nm thick green first emitting layer was formed by co-depositing GH-1 material as the main body and GD-1 material as the dopant at a mass ratio of approximately 10%. A 20 nm thick TmPyPB material was then vacuum-deposited on top of this to form the first electron transport layer. Next, a 10 nm thick N-type charge generation layer was formed on the first electron transport layer by co-depositing BPhen material as the main body and Li material as the dopant at a mass ratio of approximately 2%. A 5 nm thick P-type charge generation layer was then vacuum-deposited on top of this layer by HAT-CN material. This P-type charge generation layer also serves as the second hole injection layer. Subsequently, a 50 nm thick NPB material was vacuum-deposited to form the second hole transport layer. On top of this, a 20 nm thick green second emitting layer was formed by co-depositing GH-1 material as the main body and GD-1 material as the dopant at a mass ratio of approximately 10%. Subsequently, a second electron transport layer with a thickness of 20 nm was formed by co-depositing Liq material as a dopant at a mass ratio of approximately 33% using TmPyPB material as the main body. LiF material was then vacuum-deposited on top of this layer to form an electron injection layer with a thickness of 1 nm. Following this, a 50 nm thick Al layer was deposited to form the cathode, thus completing the fabrication of the tandem organic light-emitting diode (OLED). The structures of the HAT-CN, NPB, GH-1, GD-1, TmPyPB, BPhen, and Liq materials used to fabricate the OLED are shown in Table 1.

[0353] [Table 1]

[0354]

[0355] Comparative Examples 2 to 10

[0356] Organic light-emitting elements were prepared in the same manner as in Comparative Example 1, except that comparative compounds 1 to 9 in Table 2 were used instead of BPhen as the host of the N-type charge generation layer.

[0357] [Table 2]

[0358]

[0359] Examples 1 to 30

[0360] Organic light-emitting elements were prepared in the same manner as in Comparative Example 1, except that the compounds of Synthetic Examples 1 to 30 were used instead of BPhen as the host of the N-type charge generation layer.

[0361] The driving voltage, current efficiency, and lifetime of the fabricated organic light-emitting elements were evaluated. The evaluation results are shown in Table 3.

[0362] [Table 3]

[0363]

[0364]

[0365] As shown in Table 3 above, it can be seen that the organic light-emitting elements of the embodiments have lower driving voltages and better efficiency and lifespan compared with the organic light-emitting elements of the comparative examples.

[0366] Specific observation of the comparative examples and compounds reveals that, compared to BPhen, the introduction of rigid fluorene substituents into 1,10-phenanthroline results in a lower driving voltage and improved efficiency and lifetime. However, when fluorene is substituted with alkyl or heteroaryl groups, as shown in comparative compounds 1 and 2, the improvement in device performance is limited. This may be due to their lower thermal stability and insufficient packing density, hindering smooth intermolecular filling.

[0367] Furthermore, when fluorene is not bonded to the N atom of 1,10-phenanthroline in an adjacent position, such as in compounds 3 and 4, the improvement in performance, such as efficiency, is relatively small. This is thought to be due to limited conjugation extension, resulting in a relatively high structural RE value. When 1,10-phenanthroline is bonded to the lower side of fluorene rather than the upper side, such as in compounds 5 to 9, the improvement in element performance is also limited. This is also thought to be due to a relatively high structural RE value.

[0368] Table 4 below shows the RE values ​​calculated at the DFT b3lyp / 6-31g(d) level using the Gaussian 09W program. Comparing the RE values ​​of the compounds of the present invention with those of comparative compounds that differ only in their actual bonding positions confirms that the RE values ​​of the compounds of the present invention are lower than those of the comparative compounds.

[0369] [Table 4]

[0370]

[0371] The novel compounds of the present invention described above are particularly suitable for N-type charge-generating layers because they can be readily combined with dopants such as lithium and ytterbium by introducing 1,10-phenanthroline with non-shared electron pairs, and have excellent thermal stability by introducing rigid fluorene substituents.

[0372] Furthermore, the novel compound of the present invention has a reverse structure in which 1,10-phenanthroline is bonded to a phenyl or naphthyl group above diphenylfluorene or naphthylphenylfluorene, thus having a lower RE (recombination energy) value compared to the structure bonded to the fluorene below, thereby improving the efficiency of the element.

[0373] Furthermore, the novel compound of this invention, due to its structure of bonding with the N atom of 1,10-phenanthroline at a position immediately adjacent to it (position 2 or 9), expands conjugation and reduces the refractive index (RE) compared to other positions, thus improving the device efficiency. Additionally, by eliminating the introduction of additional functional groups into the fluorene, the fill density and refractive index can be increased, thereby extending the device's lifetime. The novel compound of this invention can be effectively applied to one or more organic layers in the organic layers of organic light-emitting devices, including the electron transport layer (ETL), hole blocking layer (HBL), and N-type charge generation layer (N-CGL). In particular, when applied to the main body of the N-type charge generation layer in tandem organic light-emitting devices, it can achieve low voltage, high efficiency, and long lifetime.

Claims

1. A novel compound represented by the following chemical formula 1, characterized in that, <Chemical Formula 1> In the chemical formula 1, Ring A is phenyl or naphthyl. R1 can be, independently, hydrogen, deuterium, halogen, cyano, nitro, nitrile, hydroxyl, thiol, substituted or unsubstituted C0–C50 amino, substituted or unsubstituted C1–C50 alkyl, substituted or unsubstituted C1–C50 alkenyl, substituted or unsubstituted C1–C50 alkoxy, substituted or unsubstituted C1–C50 thioether, substituted or unsubstituted C0–C50 silyl, substituted or unsubstituted C3–C50 cycloalkyl, substituted or unsubstituted... The following groups may be substituted C2-C50 heterocyclic alkyl groups, substituted or unsubstituted C3-C50 cycloalkenyl groups, substituted or unsubstituted C1-C30 phosphinoalkyl groups, substituted or unsubstituted C2-C50 heterocyclic alkenyl groups, substituted or unsubstituted C6-C50 aryl groups, substituted or unsubstituted C6-C50 aryloxy groups, substituted or unsubstituted C2-C50 heteroaryloxy groups, or substituted or unsubstituted C2-C50 heteroaryl groups, wherein adjacent groups may or may not combine to form a substituted or unsubstituted ring. L can be a direct bond, a substituted or unsubstituted C6-C50 arylene, or a substituted or unsubstituted C2-C50 heteroarylene. R2 through R5 are each independently hydrogen or deuterium, or adjacent groups may or may not combine to form a ring substituted or unsubstituted with one or more deuterium atoms. a is an integer from 0 to 7. b is an integer from 0 to 3. c is an integer from 0 to 6. d and e are each independent integers from 0 to 4. f is an integer from 0 to 5.

2. The novel compound according to claim 1, characterized in that, The chemical formula 1 is one of the following chemical formulas 2 to 4: <Chemical Formula 2> <Chemical Formula 3> <Chemical Formula 4> In chemical formulas 2 to 4, the definitions of R1, L, R2 to R5, and a to f are the same as those in chemical formula 1.

3. The novel compound according to claim 2, characterized in that, The chemical formula 1 is one of the following chemical formulas 2-1 to 2-3, 3-1 to 3-3, 4-1 and 4-2: <Chemical Formula 2-1> <Chemical Formula 2-2> <Chemical Formula 2-3> <Chemical Formula 3-1> <Chemical Formula 3-2> <Chemical Formula 3-3> <Chemical Formula 4-1> <Chemical Formula 4-2> In chemical formulas 2-1 to 2-3, 3-1 to 3-3, 4-1 and 4-2, the definitions of R1, L, R2 to R5 and a to f are the same as in chemical formula 1.

4. The novel compound according to claim 1, characterized in that, The chemical formula 1 is the following chemical formula 5: <Chemical Formula 5> In chemical formula 5, the definitions of L, R2 to R5, and b to f are the same as in chemical formula 1. R1 is one of hydrogen, deuterium, methyl, -CD3, phenyl, biphenyl, naphthyl, pyridyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinazolinyl, and naphthidyl.

5. The novel compound according to claim 1, characterized in that, One or more groups in R3, R4 and R5 are bonded to each other to form a benzene ring that is substituted with or unsubstituted with one or more deuterium groups.

6. The novel compound according to claim 5, characterized in that, The fluorene portion in chemical formula 1 is one of the following structural formulas F-1 to F-5: <Structural Formula F-1> <Structural Formula F-2> <Structural Formula F-3> <Structural Formula F-4> <Structural Formula F-5> In the structural formulas F-1 to F-5, ring A is defined as shown in chemical formula 1. R2 to R5 and R7 are each independently either hydrogen or deuterium. The definitions of c to f are shown in Chemical Formula 1. h is an independent integer from 0 to 6. This indicates the bonding position between it and the linking group L in chemical formula 1.

7. The novel compound according to claim 1, characterized in that, The chemical formula 1 is one of the following chemical formulas A to H: <Chemical Formula A> <Chemical Formula B> <Chemical Formula C> <Chemical Formula D> <Chemical Formula E> <Chemical Formula F> <Chemical Formula G> <Chemical Formula H> In the chemical formulas A to H, the definitions of R1, L and b are the same as in chemical formula 1.

8. The novel compound according to claim 1, characterized in that, The compound represented by chemical formula 1 is selected from one of the following compounds 1 to 543: 。 9. An organic light-emitting element, characterized in that, include: First electrode and second electrode; as well as At least one organic layer disposed between the first electrode and the second electrode. The at least one organic layer comprises a compound according to any one of claims 1 to 8.

10. The organic light-emitting element according to claim 9, characterized in that, The organic layer containing the compound is at least one of an electron transport layer, a hole blocking layer, and a charge generating layer.

11. A series-connected organic light-emitting element, characterized in that, include: First electrode and second electrode; Multiple light-emitting portions located between the first electrode and the second electrode; as well as A charge generation layer located at one or more sites between two adjacent luminescent portions. Wherein, at least one of the charge generation layers includes an N-type charge generation layer, the N-type charge generation layer comprising a compound represented by the following chemical formula 1 and a dopant: <Chemical Formula 1> In the chemical formula 1, Ring A is phenyl or naphthyl. R1 can be, independently, hydrogen, deuterium, halogen, cyano, nitro, nitrile, hydroxyl, thiol, substituted or unsubstituted C0–C50 amino, substituted or unsubstituted C1–C50 alkyl, substituted or unsubstituted C1–C50 alkenyl, substituted or unsubstituted C1–C50 alkoxy, substituted or unsubstituted C1–C50 thioether, substituted or unsubstituted C0–C50 silyl, substituted or unsubstituted C3–C50 cycloalkyl, substituted or unsubstituted... The following groups may be substituted C2-C50 heterocyclic alkyl groups, substituted or unsubstituted C3-C50 cycloalkenyl groups, substituted or unsubstituted C1-C30 phosphinoalkyl groups, substituted or unsubstituted C2-C50 heterocyclic alkenyl groups, substituted or unsubstituted C6-C50 aryl groups, substituted or unsubstituted C6-C50 aryloxy groups, substituted or unsubstituted C2-C50 heteroaryloxy groups, or substituted or unsubstituted C2-C50 heteroaryl groups, wherein adjacent groups may or may not combine to form a substituted or unsubstituted ring. L can be a direct bond, a substituted or unsubstituted C6-C50 arylene, or a substituted or unsubstituted C2-C50 heteroarylene. R2 through R5 are each independently hydrogen or deuterium, or adjacent groups may or may not combine to form a ring substituted or unsubstituted with one or more deuterium atoms. a is an integer from 0 to 7. b is an integer from 0 to 3. c is an integer from 0 to 6. d and e are each independent integers from 0 to 4. f is an integer from 0 to 5.

12. The tandem organic light-emitting element according to claim 11, characterized in that, The dopant includes at least one selected from lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), ytterbium (Yb), samarium (Sm), tin (Sn), copper (Cu), titanium (Ti), cadmium (Cd), mercury (Hg), lead (Pb), bismuth (Bi), zinc (Zn), iron (Fe), cobalt (Co), nickel (Ni), indium (In), gallium (Ga), thorium (Th), uranium (U), silver (Ag), aluminum (Al), gold (Au), molybdenum (Mo), niobium (Nb), palladium (Pd), platinum (Pt), and europium (Eu).

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