Organic compound and organic electroluminescent device using the same

Abstract

The present invention relates to a novel compound having excellent carrier transport ability, light emitting ability, and thermal stability, and to an organic electroluminescence device having improved properties such as light emitting efficiency, driving voltage, and lifespan by incorporating the compound in one or more organic layers.

Description

[Technical Field]

[0001] The present invention relates to a novel organic light-emitting compound and an organic electroluminescence device using the same, and more particularly to a compound having excellent electron transport ability, and an organic electroluminescence device having improved properties such as luminous efficiency, driving voltage, and lifespan by incorporating the compound in one or more organic material layers. [Background technology]

[0002] When a voltage is applied between two electrodes in an organic electroluminescent device, holes are injected into the organic layer from the anode, and electrons are injected into the organic layer from the cathode. The injected holes and electrons combine to form excitons, which emit light when they return to the ground state. The materials used in the organic layer can be classified according to their functions into light-emitting materials, hole-injecting materials, hole-transporting materials, electron-transporting materials, electron-injecting materials, etc.

[0003] Depending on the emitted color, luminescent materials are divided into blue, green, and red luminescent materials, and yellow and orange luminescent materials for achieving more natural colors. In addition, a host / dopant system can be used as the luminescent material to improve color purity and luminous efficiency through energy transfer.

[0004] Dopant materials are divided into fluorescent dopants that use organic materials and phosphorescent dopants that use metal complex compounds containing heavy atoms such as Ir and Pt. In this regard, the development of phosphorescent materials can theoretically improve luminous efficiency by up to four times compared to fluorescence, so much research is being conducted not only on phosphorescent dopants but also on phosphorescent host materials.

[0005] Currently, NPB, BCP, and Alq3 are widely known as materials for hole injection layers, hole transport layers, hole blocking layers, and electron transport layers, while anthracene derivatives have been reported as materials for light-emitting layers. In particular, metal complex compounds containing Ir, such as Firpic, Ir(ppy)3, and (acac)Ir(btp)2, which have the advantage of improving efficiency, are used as blue, green, and red phosphorescent dopants, and 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent host material.

[0006] However, although conventional organic layer materials are advantageous in terms of light-emitting properties, they have low glass transition temperatures and very poor thermal stability, which means that the lifespan of organic electroluminescent devices is not at a satisfactory level. Therefore, there is a demand for the development of organic layer materials with excellent performance. Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has as its technical object the provision of a novel compound that has excellent heat resistance, carrier transport ability, light-emitting ability, and the like and can be used as an organic layer material for an organic electroluminescence device, specifically as an electron transport layer, an electron transport auxiliary layer, or a light-emitting layer.

[0008] Another technical object of the present invention is to provide an organic electroluminescence device that contains the novel compound and thereby has a low driving voltage, high luminous efficiency, and an improved lifespan.

[0009] Other objects and advantages of the present invention will be more clearly set forth in the detailed description of the invention and claims that follow. [Means for solving the problem]

[0010] In order to achieve the above object, the present invention provides a compound represented by the following Chemical Formula 1:

[0011] [ka]

[0012] In the above Chemical Formula 1, X1 to X3 are the same or different and each independently represent C(R6) or N, provided that at least two of X1 to X3 represent N; Y1 and Y2 are the same or different and each independently represents O, S, or NR 11 selected from the group consisting of Ar1 and Ar2 are the same or different and each independently represent C1 to C 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C3-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphine groups, C6-C 60 arylphosphine oxide groups, and C6-C 60 or which may be joined to any adjacent group to form a fused ring; R1 to R6 and R 11 are the same or different and each independently represent hydrogen, deuterium (D), halogen, cyano group, nitro group, C1 to C 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C3-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphine groups, C6-C 60 arylphosphine oxide groups, and C6-C 60 or which may be joined to any adjacent group to form a fused ring; L is C6~C 18 and heteroarylene groups having 5 to 18 ring atoms, a is an integer of 1 to 5, and when a is 2 or more, multiple Ls are the same or different; o, p, q, and s are each independently an integer of 0 to 4, and r is an integer of 0 to 3; The arylene group and heteroarylene group of L, and the Ar1 to Ar2, R1 to R6, and R 11 The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group, and arylamine group each independently include deuterium (D), halogen, cyano group, nitro group, C1 to C6 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40Alkyloxy groups, C6-C 60 Aryloxy groups, C1-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphine groups, C6-C 60 arylphosphine oxide groups, and C6-C 60 In this case, when there are a plurality of the substituents, they may be the same or different.

[0013] The present invention also provides an organic electroluminescence device comprising an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers comprises a compound represented by Chemical Formula 1.

[0014] The organic layer containing the compound represented by Chemical Formula 1 may be selected from the group consisting of an emitting layer, an emitting auxiliary layer, a hole injection layer, a hole transport layer, an electron injection layer, a life improvement layer, an electron transport layer, and an electron transport auxiliary layer. In this case, the compound represented by Chemical Formula 1 may be included as a phosphorescent host material in the emitting layer, a material in the electron transport layer, and a material in the electron transport auxiliary layer. [Effects of the Invention]

[0015] According to one embodiment of the present invention, the compound represented by Chemical Formula 1 has excellent electron transporting ability, light emitting ability, heat resistance, etc., and can be used as an organic layer material for an organic electroluminescence device.

[0016] In particular, when the compound represented by Chemical Formula 1 of the present invention is used as an electron transport layer or electron transport auxiliary layer material, it can exhibit higher thermal stability, lower driving voltage, higher mobility, higher current efficiency, and longer life properties than conventional host materials or electron transport materials.

[0017] As a result, the organic electroluminescence device including the compound represented by Chemical Formula 1 can be significantly improved in terms of excellent light-emitting performance, low driving voltage, long life, and high efficiency, and can therefore be effectively applied to full-color display panels, etc.

[0018] The effects of the present invention are not limited to the above-mentioned examples, and various other effects are included in this specification. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below.

[0020] <New organic compounds> The present invention provides novel aryl compounds, such as polycyclic spiro compounds, which have excellent thermal stability, carrier transport ability, and light-emitting ability.

[0021] The compound represented by Chemical Formula 1 comprises a core having a spiro bond structure with excellent conductivity containing at least two heteroatoms (e.g., OO / SS / OS / S-NR' / NR'-NR'' / O-NR') and an electron-withdrawing group (EWG) with excellent electron transport ability, which are bonded via a linker (L) to form a basic skeleton structure.

[0022] Typically, in the light-emitting layer of an organic light-emitting device, electrons and holes combine to generate excitons. If the layers adjacent to the light-emitting layer are unable to block these generated excitons, the efficiency of the device decreases. Furthermore, if holes generated in the hole-injection layer and intended for the light-emitting layer migrate to the electron-injection layer, the efficiency and lifetime of the device decrease. In this case, if the organic material constituting the electron-transporting auxiliary layer or electron-transporting layer adjacent to the light-emitting layer has high singlet energy, triplet energy, and low HOMO energy, it can effectively block the migration of excitons and holes generated in the light-emitting layer to the electron-transporting layer. This effect is particularly evident in devices using phosphorescent emitters compared to devices using fluorescent emitters.

[0023] In the present invention, in order to solve the above-mentioned problems, a cyclic compound-based core (core) having excellent conductivity is structurally distorted to have higher singlet energy and triplet energy, and at least one arylene / heteroarylene-based linker (L) is introduced between the core and the EWG group having excellent electron transport ability, thereby improving the safety of the molecule.

[0024] The use of a spiro skeleton as the core structure allows for a high glass transition temperature (Tg) and excellent thermal stability. Furthermore, the introduction of triazine or pyrimidine, a functional group with strong electron-withdrawing ability, to improve the electron transfer rate provides physicochemical properties more suitable for electron injection and electron transport. Furthermore, the compound of Chemical Formula 1 has an electron-donating effect due to the lone electron pair of the heteroatom (O or S) contained in the polycyclic spiro core structure. Therefore, when such a compound is applied to an organic light-emitting device, the luminous efficiency of the device can be improved, and the durability and stability of the device can be enhanced, effectively extending the device's lifespan. When such a compound of Chemical Formula 1 is used as a material for an electron transport layer or electron transport auxiliary layer, it can efficiently accept electrons from the cathode, thereby smoothly transporting electrons to the light-emitting layer, thereby reducing the device's driving voltage and achieving high efficiency and long lifespan.

[0025] Furthermore, the compound represented by Chemical Formula 1 of the present invention has a higher triplet energy than the light-emitting layer, thereby preventing excitons generated in the light-emitting layer from diffusing (moving) to the adjacent electron transport layer or hole transport layer. This increases the number of excitons contributing to light emission, improving the luminous efficiency of the device, enhancing the durability and stability of the device, and effectively extending the device's lifespan. Most of the developed materials exhibit physical characteristics that allow for low-voltage operation and improved lifespan.

[0026] As described above, when the compound represented by Chemical Formula 1 of the present invention is used as an organic layer material of an organic electroluminescent device, preferably as an emitting layer material (blue, green, and / or red phosphorescent host material), an electron transport layer / injection layer material, a hole transport layer / injection layer material, an emitting auxiliary layer material, or a lifetime improvement layer material, the performance and lifetime characteristics of the organic electroluminescent device can be significantly improved. In particular, when the compound of the present invention is used as an electron transport layer or electron transport auxiliary layer material, significant performance improvements can be expected in terms of device efficiency, driving voltage, and lifetime characteristics. As a result, such an organic electroluminescent device can maximize the performance of a full-color organic light-emitting panel.

[0027] According to the present invention, the compound represented by Chemical Formula 1 comprises a polycyclic spirobixanthene core having excellent conductivity and a nitrogen-containing heteroaromatic ring (e.g., azine, X1-X3-containing ring) having electron-withdrawing group (EWG) characteristics having excellent electron transport ability, and a linker (L) is bonded between them to form a basic skeleton structure.

[0028] The polycyclic spiro core structure includes at least two heteroatoms (e.g., Y1-Y2 containing rings). According to one embodiment of such a polycyclic spiro core structure, Y1 and Y2 are the same or different and each independently represent O, S, and NR 11 is selected from the group consisting of:

[0029] where R 11 is hydrogen, deuterium (D), halogen, cyano group, nitro group, C1-C 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C3-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphine groups, C6-C 60 arylphosphine oxide groups, and C6-C 60 or which may be combined with any adjacent group to form a fused ring. 11 If there are multiple R 11 may be the same or different. 11 are hydrogen, deuterium (D), C1 to C 40 Alkyl groups of C6 to C 60 and heteroaryl groups having 5 to 60 ring atoms.

[0030] According to one embodiment, the polycyclic spirocore (e.g., Y1-Y2 containing ring) structure may be further embodied in any one of the following structural formulae, including, but not limited to:

[0031] [ka]

[0032] In the above formula, * means a linking site to Chemical Formula 1; R 11 are hydrogen, deuterium (D), C1 to C 40 Alkyl groups of C6 to C 60 and heteroaryl groups having 5 to 60 ring atoms, R1 to R4, o, p, q, and r are each defined as in Chemical Formula 1.

[0033] The polycyclic spiro core (for example, the ring containing Y1 and Y2) may be substituted with various substituents, each of which may be R1 to R4. R1 to R4 may be the same or different and each independently represent hydrogen, deuterium (D), halogen, cyano, nitro, C1 to C2, or the like. 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C3-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphine groups, C6-C 60 arylphosphine oxide groups, and C6-C 60 or these may be bonded to any adjacent group to form a condensed ring. In this case, when there are multiple R1 to R4, the multiple R1 to R4 may be the same or different from each other. Specifically, R1 to R4 may be the same or different from each other and each independently represent hydrogen, deuterium (D), a cyano group, C1 to C 40 Alkyl groups of C6 to C 60and heteroaryl groups having 5 to 60 ring atoms, or are preferably fused rings formed by bonding these with adjacent groups.

[0034] Here, o, p, q, and r are each independently an integer of 0 to 4, and r may be an integer of 0 to 3. When o is 0, R1 is hydrogen, and when o is 1 to 3, R1 may have the above-mentioned substituents excluding hydrogen. p, q, and r are similarly applicable.

[0035] In Chemical Formula 1 according to the present invention, a nitrogen-containing heteroaromatic ring (e.g., azine, ring containing X1 to X3) having excellent electron transport ability and EWG properties is linked to one phenyl ring of the polycyclic spirocore structure (e.g., ring containing Y1 to Y2) via a linker (L).

[0036] The nitrogen-containing heterocycle (e.g., a ring containing X1 to X3) is a monocyclic or polycyclic nitrogen-containing heteroaryl group containing at least two nitrogen atoms. According to one embodiment of the nitrogen-containing heteroaromatic ring, X1 to X3 are the same or different and each independently represent C(R6) or N, provided that at least two of X1 to X3 contain N. Specifically, it is preferable that the ring contains two to three N atoms. By containing such a heterocycle containing two or three nitrogen atoms, the ring exhibits better electron absorption properties and is advantageous for electron injection and transport.

[0037] where R6 is hydrogen, deuterium (D), C1-C 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C3-C 40 Alkylsilyl groups, C6-C 60Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphanyl groups, C6-C 60 Monoarylphosphinyl groups, C6-C 60 Diarylphosphinyl groups, C6-C 60 Arylamine groups, C5-C 60 and heteroarylamine groups having 5 to 60 ring atoms, or these may be bonded to any adjacent group to form a condensed ring. In this case, when there are multiple R6, the multiple R6 may be the same or different from each other. Specifically, R6 is selected from the group consisting of hydrogen, deuterium (D), C1 to C 40 Alkyl groups of C6 to C 60 and heteroaryl groups having 5 to 60 ring atoms.

[0038] According to one specific example, the nitrogen-containing heterocycle (e.g., X1-X3-containing ring) may be further embodied as any one selected from the following structural formulae, but is not limited thereto:

[0039] [ka]

[0040] In the above formula, * means a linking site to Chemical Formula 1; W is O or S; Ar1 and Ar2 are defined as in Chemical Formula 1.

[0041] The nitrogen-containing heterocycle (for example, a ring containing X1 to X3) may be substituted with various substituents, such as Ar1 and Ar2. Ar1 and Ar2 may be the same or different and each independently represent a C1 to C 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C3-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphine groups, C6-C 60 arylphosphine oxide groups, and C6-C 60 or these may be bonded to any adjacent group to form a fused ring. Specifically, Ar1 and Ar2 are each independently selected from the group consisting of C6 to C 60 or a heteroaryl group having 5 to 60 ring atoms, preferably a C6 to C 40 or a heteroaryl group having 5 to 40 ring atoms.

[0042] According to one embodiment, Ar1 and Ar2 may be the same or different and may each independently be embodied as any one of the following structural formulae, but are not limited thereto:

[0043] [ka]

[0044] [ka]

[0045] * denotes a linking site to Chemical Formula 1. Although not shown in the structural formula, the compound may be substituted with at least one substituent known in the art (e.g., the same as the definition of R5).

[0046] In the compound represented by Chemical Formula 1 according to the present invention, a polycyclic spiro core (e.g., a ring containing Y1-Y2) with excellent conductivity and a nitrogen-containing heteroaromatic ring (e.g., an azine or a ring containing X1-X3) with excellent electron transport properties and EWG characteristics are connected via another linker (e.g., L). The presence of this linker (L) expands the HOMO region, providing advantages to the HOMO-LUMO distribution and enhancing charge transfer efficiency through appropriate HOMO-LUMO overlap. It also enhances the stability of the molecule.

[0047] The linker (e.g., L) is not particularly limited and may be a linker of a common divalent group well known in the art. Specifically, L may be a single bond or a C6 to C 18 and heteroarylene groups having 5 to 18 ring atoms. More specifically, 12 and heteroarylene groups having 5 to 12 ring atoms. Here, the number of linkers (a) is an integer of 1 to 5, and specifically, preferably 1 to 3. Here, when a is 1 to 5, multiple Ls may be the same or different.

[0048] Specific examples of the arylene group linker include a phenylene group, a biphenylene group, a naphthylene group, an anthracenylene group, an indenylene group, a pyrantrenylene group, a carbazolylene group, a thiophenylene group, an indolylene group, a prinylene group, a quinolinylene group, a pyrrolylene group, an imidazolylene group, an oxazolylene group, a thiazolylene group, a pyridinylene group, and a pyrimidinylene group. More specifically, a phenylene group or a biphenylene group is preferred. Specific examples of the heteroarylene group linker include a pyrrole-based moiety, a furan-based moiety, a thiophene-based moiety, a pyridine-based moiety, a pyrimidine-based moiety, a pyrazine-based moiety, a triazine-based moiety, a dibenzofuran-based moiety, a dibenzothiophene-based moiety, and / or a dibenzoselenophenone-based moiety.

[0049] According to one embodiment, L may be a linking group selected from the following structural formulas:

[0050] [ka]

[0051] In the above formula, * denotes a linking site to Chemical Formula 1. Although not shown in the structural formula, the compound may be substituted with at least one substituent known in the art (e.g., the same as the definition of R5).

[0052] Furthermore, the linker (e.g., L) may have various substituents at R5, where R5 is hydrogen, deuterium (D), C1 to C6, 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C3-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60 Arylphosphanyl groups, C6-C 60 Monoarylphosphinyl groups, C6-C 60 Diarylphosphinyl groups, C6-C 60 Arylamine groups, C5-C 60and heteroarylamine groups having 5 to 60 ring atoms, or these may be bonded to any adjacent group to form a condensed ring. In this case, when there are multiple R5, the multiple R5 may be the same or different from each other. Specifically, R5 is selected from the group consisting of hydrogen, deuterium (D), C1 to C 40 Alkyl groups of C6 to C 60 and heteroaryl groups having 5 to 60 ring atoms.

[0053] Here, s may be an integer of 0 to 4. In this case, when s is 0, R5 is hydrogen, and when s is 1 to 4, R5 may have the above-mentioned substituents excluding hydrogen.

[0054] In the above-mentioned Chemical Formula 1, the arylene group and heteroarylene group of L, and the Ar1 to Ar2, R1 to R6, and R 11 The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group, and arylamine group each independently include deuterium (D), halogen, cyano group, nitro group, C1 to C6 40 Alkyl groups of C2 to C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Cycloalkyl groups, heterocycloalkyl groups with 3 to 40 atoms, C6 to C 60 aryl groups, heteroaryl groups with 5 to 60 ring atoms, C1 to C 40 Alkyloxy groups, C6-C 60 Aryloxy groups, C1-C 40 Alkylsilyl groups, C6-C 60 Arylsilyl groups, C1-C 40 Alkylboron groups, C6-C 60 Arylboron groups, C6-C 60Arylphosphine groups, C6-C 60 arylphosphine oxide groups, and C6-C 60 In this case, when there are a plurality of the substituents, they may be the same or different.

[0055] According to one embodiment of the present invention, the compound represented by Chemical Formula 1 may be further embodied as any one of the following Chemical Formulas 2 to 10, depending on the type of heteroatom introduced into the polycyclic spiro core structure, but is not limited thereto.

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] In the above formula, X1~X3, Ar1~Ar2, L, R1~R5, R 11 , o, p, q, r, s, and a are each defined as in Chemical Formula 1.

[0066] According to another embodiment of the present invention, the compound represented by Chemical Formula 1 may be further embodied as any one of the following Chemical Formulas 11 to 29 depending on the type of nitrogen-containing heterocycle (e.g., X1 to X3-containing ring), but is not limited thereto.

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073]

change

[0074]

change

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

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[0084] [ka]

[0085] [ka]

[0086] In the above formula, Y1 to Y2, Ar1 to Ar2, L, R1 to R5, o, p, q, r, s, and a are each defined as in Chemical Formula 1.

[0087] According to another embodiment of the present invention, the compound represented by Chemical Formula 1 may be further embodied as any one of the following Chemical Formulae 30 to 37, depending on the bonding position of the fused ring formed in the polycyclic spiro core, but is not limited thereto.

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] In the above formula, Ring A may be a typical hydrocarbon ring or a hydrocarbon ring containing one or more heteroatoms as known in the art, which may be fused, bridged, or spirocyclically bonded to another adjacent ring (e.g., core structure). For example, ring A may be selected from the group consisting of a monocyclic or polycyclic alicyclic ring, a monocyclic or polycyclic heteroalicyclic ring, a monocyclic or polycyclic aromatic ring, or a monocyclic or polycyclic heteroaromatic ring. Specifically, ring A may be a C6-C 18 or a heteroaromatic ring having 5 to 18 ring atoms.

[0097] X1 to X3, Y1 to Y2, Ar1 to Ar2, L, R1 to R5, o, p, q, r, s, and a are each defined as in Chemical Formula 1.

[0098] According to yet another embodiment of the present invention, the compound represented by Chemical Formula 1 may be further embodied as any one of the following Chemical Formulas 38 to 40, depending on the bonding position of the nitrogen-containing heterocycle, but is not limited thereto.

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] In the above formula, X1 to X3, Y1 to Y2, Ar1 to Ar2, L, R1 to R5, o, p, q, r, s, and a are each defined as in Chemical Formula 1.

[0103] According to another embodiment of the present invention, the compound represented by Formula 1 may be further embodied as Formula 41 or Formula 42 below depending on the type of linker (L), but is not limited thereto.

[0104] [ka]

[0105] [ka]

[0106] In the above formula, Z is O or S; X1 to X3, Y1 to Y2, Ar1 to Ar2, R1 to R5, o, p, q, r, s, and a are each defined as in Chemical Formula 1.

[0107] The compound represented by Chemical Formula 1 according to the present invention described above may be further embodied as any one of the following compounds 1 to 100. However, the compound represented by Chemical Formula 1 according to the present invention is not limited to the following examples.

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] In the present invention, the "number of ring atoms" refers to the number of ring atoms constituting the cyclic structure, and the ring atom may refer to carbon or a heteroatom selected from the group consisting of N, O, S, and Se. For example, the number of ring atoms in pyridine is 6, including 5 C atoms and 1 N atoms constituting the pyridine ring.

[0114] In the present invention, "alkyl" means a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0115] In the present invention, "alkenyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0116] In the present invention, "alkynyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0117] In the present invention, the term "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms, which is a single ring or a combination of two or more rings. It may also include a form in which two or more rings are pendant or fused to each other. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, etc.

[0118] In the present invention, the term "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 ring atoms. In this case, one or more carbon atoms, preferably 1 to 3 carbon atoms, in the ring are substituted with a heteroatom such as N, O, S, or Se. In addition, the term may include a form in which two or more rings are pendant or fused to each other, and may further include a form in which two or more rings are fused to an aryl group. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.

[0119] In the present invention, "aryloxy" refers to a monovalent substituent represented by RO-, where R means an aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0120] In the present invention, "alkyloxy" refers to a monovalent substituent represented by R'O-, where R' is an alkyl having 1 to 40 carbon atoms and may have a linear, branched, or cyclic structure. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, and pentoxy.

[0121] In the present invention, the term "arylamine" refers to an amine substituted with an aryl having 6 to 40 carbon atoms.

[0122] In the present invention, the term "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0123] In the present invention, "heterocycloalkyl" refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 ring atoms, in which one or more carbon atoms, preferably 1 to 3 carbon atoms in the ring, are substituted with a heteroatom such as N, O, S, or Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

[0124] In the present invention, "alkylsilyl" means silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 5 to 40 carbon atoms.

[0125] In the present invention, the term "fused ring" means a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combination thereof.

[0126] <Electron transport layer material> The present invention provides an electron transport layer comprising the compound represented by Chemical Formula 1.

[0127] The electron transport layer (ETL) serves to transport electrons injected from the cathode to an adjacent layer, specifically the light-emitting layer.

[0128] The compound represented by Chemical Formula 1 may be used alone as an electron transport layer (ETL) material, or may be used in combination with electron transport layer materials known in the art, but is preferably used alone.

[0129] Electron transport layer materials that can be used with the compound of Formula 1 include conventional electron transport materials known in the art. Examples of usable electron transport materials include, but are not limited to, oxazole-based compounds, isoxazole-based compounds, triazole-based compounds, isothiazole-based compounds, oxadiazole-based compounds, thiadiazole-based compounds, perylene-based compounds, aluminum complexes (e.g., Alq3 (tris(8-quinolinolato)-aluminum), BAlq, SAlq, Almq3), and gallium complexes (e.g., Gaq'2OPiv, Gaq'2OAc, and 2(Gaq'2)). These may be used alone or in combination.

[0130] In the present invention, when the compound of Chemical Formula 1 and the electron transport layer material are used in combination, the mixing ratio thereof is not particularly limited and can be appropriately adjusted within a range known in the art.

[0131] <Electron transport auxiliary layer material> The present invention also provides an electron transporting auxiliary layer comprising the compound represented by Chemical Formula 1.

[0132] The electron transport auxiliary layer is disposed between the light emitting layer and the electron transport layer and serves to prevent excitons or holes generated in the light emitting layer from diffusing into the electron transport layer.

[0133] The compound represented by Chemical Formula 1 may be used alone as the electron transport auxiliary layer material, or may be used in combination with an electron transport layer material known in the art, but is preferably used alone.

[0134] Materials for the electron transporting auxiliary layer that can be mixed with the compound of Formula 1 include conventional electron transporting materials known in the art, such as oxadiazole derivatives, triazole derivatives, pentane derivatives (e.g., BCP), and nitrogen-containing heterocyclic derivatives.

[0135] In the present invention, when the compound of Chemical Formula 1 and the electron transport auxiliary layer material are used in combination, the mixing ratio thereof is not particularly limited and can be appropriately adjusted within a range known in the art.

[0136] <Organic electroluminescence element> Another aspect of the present invention relates to an organic electroluminescence device (organic EL device) containing the compound represented by Chemical Formula 1 according to the present invention.

[0137] Specifically, the present invention provides an organic electroluminescence device including an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers contains a compound represented by Chemical Formula 1. In this case, the compound may be used alone or in combination of two or more.

[0138] The one or more organic material layers may be one or more of a hole injection layer, a hole transport layer, an emitting layer, an emitting auxiliary layer, a lifetime improving layer, an electron transport layer, an electron transport auxiliary layer, and an electron injection layer, and at least one of the organic material layers contains the compound represented by Chemical Formula 1. Specifically, the organic material layer containing the compound of Chemical Formula 1 may be an emitting layer, an emitting auxiliary layer, an electron transport layer, an electron transport auxiliary layer, and / or a lifetime improving layer, and more specifically, it is preferably an electron transport layer or an electron transport auxiliary layer.

[0139] The light-emitting layer of the organic electroluminescent device according to the present invention contains a host material and a dopant material, and in this case, the host material may contain the compound of Chemical Formula 1. Furthermore, the light-emitting layer of the present invention may contain, in addition to the compound of Chemical Formula 1, a compound known in the art as a host.

[0140] When the compound represented by Chemical Formula 1 is contained as an emission layer material of an organic electroluminescent device, preferably as a blue, green, or red phosphorescent host material, the binding strength between holes and electrons in the emission layer is increased, thereby improving the efficiency (light-emitting efficiency and power efficiency), lifespan, brightness, driving voltage, etc. of the organic electroluminescent device. Specifically, the compound represented by Chemical Formula 1 is preferably contained in the organic electroluminescent device as a green and / or red phosphorescent host, fluorescent host, or dopant material. In particular, the compound represented by Chemical Formula 1 of the present invention is preferably an exciplex N-type host material for green phosphorescence in an emission layer with high efficiency.

[0141] The structure of the organic electroluminescent device of the present invention is not particularly limited, and may include a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a light-emitting layer, an electron transport layer, and a cathode are sequentially stacked. In this case, one or more of the hole injection layer, hole transport layer, light-emitting auxiliary layer, light-emitting layer, electron transport layer, and electron injection layer may contain the compound represented by Chemical Formula 1. Preferably, the light-emitting layer, more preferably the phosphorescent host, may contain the compound represented by Chemical Formula 1. In addition, an electron injection layer may be further stacked on the electron transport layer.

[0142] The organic electroluminescent element of the present invention may have a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic layer.

[0143] The organic electroluminescence device of the present invention can be manufactured by forming organic layers and electrodes using materials and methods known in the art, except that at least one of the organic layers contains the compound represented by Chemical Formula 1.

[0144] The organic layer may be formed by a vacuum deposition method or a solution coating method, such as, but not limited to, spin coating, deep coating, doctor blading, inkjet printing, or thermal transfer.

[0145] The substrate used in manufacturing the organic electroluminescence device of the present invention is not particularly limited, and examples thereof include, but are not limited to, silicon wafers, quartz, glass plates, metal plates, plastic films, and sheets.

[0146] The anode material may be any anode material known in the art, without limitation, including, but not limited to, metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO:Sb; conductive polymers such as polythiopene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiopene] (PEDT), polypyrrole, or polyaniline; and carbon black.

[0147] The cathode material may be any cathode material known in the art, without limitation, including, but not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; and multilayer structures such as LiF / Al or LiO / Al.

[0148] The hole injection layer, hole transport layer, electron injection layer, and electron transport layer are not particularly limited, and ordinary materials known in the art can be used without any restrictions.

[0149] The present invention will be described in detail below with reference to examples, but the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

[0150] [Preparation Examples 1-12] [Preparation example 1] Synthesis of Core1 [ka]

[0151] <Step 1> 40.0 g (133.5 mmol) of (2-bromo-5-chlorophenyl)(phenyl)sulfane was added to 400 ml of THF and cooled to -78 °C. Then, 56.1 ml (140.2 mmol) of n-BuLi (1.6 M in n-hexane) was added dropwise. The reaction solution was cooled and reacted at -78 °C for 2 hours. The reaction solution was then added dropwise via cannula to a reactor containing 26.2 g (133.5 mmol) of 9H-xanthen-9-one dissolved in 250 ml of THF at -78 °C. The mixture was then warmed to room temperature and reacted for 4 hours. After completion of the reaction, 400 ml of H2O and 400 ml of ethyl acetate were added, and the organic layer was extracted. The organic layer was then treated with MgSO4 to remove water and filtered. The filtrate was concentrated under reduced pressure to obtain 50.1 g (90% yield) of 9-(5-chloro-2-(phenylthio)phenyl)-9H-xanthen-9-ol.

[0152] <Step 2> 50.1 g (120.2 mmol) of 9-(5-chloro-2-(phenylthio)phenyl)-9H-xanthen-9-ol was added to 350 ml of AcOH, and 50 ml of HCl was added. The mixture was stirred under reflux for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, and the resulting solid was filtered and washed with 200 ml of HO. The solid was dissolved in dichloromethane, treated with MgSO4 to remove anhydrous ions, and then filtered. The filtrate was concentrated under reduced pressure and subjected to column chromatography to obtain 41.8 g (87.2% yield) of 2-chlorospiro[thioxanthene-9,9'-xanthene].

[0153] <Step 3> 41.8 g (104.8 mmol) of 2-chlorospiro[thioxanthene-9,9'-xanthene], 31.9 g (125.7 mmol) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.3 g (3.1 mmol) of Pd(dppf)Cl2, 30.8 g (314.4 mmol) of KOAc, and 3.0 g (6.3 mmol) of Xphos were added to 500 mL of 1,4-dioxane and heated under reflux for 12 hours. After the reaction was complete, the mixture was extracted with dichloromethane, and MgSO4 was added to remove water and then filtered. After filtration, the organic layer was concentrated under reduced pressure and purified by column chromatography using dichloromethane and hexane, followed by solidification using methanol. The solid was filtered, washed with methanol, and dried in an oven to obtain 41.8 g of Core 1 (yield 81.4%). Mass: [(M+H) + ]:491

[0154] [Preparation example 2] Synthesis of Core2 [ka]

[0155] 56.8 g (66.2% yield for the two steps) of 2-bromo-9,9'-spirobi[xanthene] was obtained in the same manner as in Steps 1 and 2 of Preparative Example 1, except that 50.0 g (200.7 mmol) of 1-bromo-2-phenoxybenzene and 55.2 g (200.7 mmol) of 2-bromo-9H-xanthen-9-one were used as starting materials.

[0156] <Step 3> 56.8 g (132.9 mmol) of 2-bromo-9,9'-spirobi[xanthene], 40.5 g (159.5 mmol) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane), 2.9 g (4.0 mmol) of Pd(dppf)Cl2, and 39.1 g (398.8 mmol) of KOAc were added to 600 mL of 1,4-dioxane and heated to reflux for 12 hours. After the reaction was complete, the mixture was extracted with dichloromethane, and MgSO4 was added to remove water and then filtered. After filtration, the organic layer was concentrated under reduced pressure and purified by column chromatography using dichloromethane and hexane, followed by solidification using methanol. The solid was filtered, washed with methanol, and dried in an oven to obtain 47.9 g of Core 2 (76.1% yield). Mass: [(M+H) + ]:475

[0157] [Preparation Example 3] Synthesis of Core3 [ka]

[0158] Core 3 (53.5 g, 48.5% yield for the three steps) was obtained in the same manner as in Step 1 and Step 2 of Preparative Example 1 and Step 3 of Preparative Example 2, except that 50.0 g (200.7 mmol) of 1-bromo-2-phenoxybenzene and 70.3 g (200.7 mmol) of 2-bromo-10-phenylacridin-9(10H)-one were used. Mass: [(M+H) + ]:550

[0159] [Preparation Example 4] Synthesis of Core4 [ka]

[0160] Core 4 (38.0 g, 41.1% yield for the three steps) was obtained in the same manner as in Step 1 and Step 2 of Preparative Example 1 and Step 3 of Preparative Example 2, except that 50.0 g (188.6 mmol) of (2-bromophenyl)(phenyl)sulfane and 51.9 g (188.6 mmol) of 2-bromo-9H-xanthen-9-one were used as starting materials. Mass: [(M+H) + ]:491

[0161] [Preparation Example 5] Synthesis of Core5 [ka]

[0162] 46.0 g of Core 5 (48.2% yield for the three steps) was obtained in the same manner as in Step 1 and Step 2 of Preparative Example 1 and Step 3 of Preparative Example 2, except that 50.0 g (188.6 mmol) of (2-bromophenyl)(phenyl)sulfane and 54.9 g (188.6 mmol) of 2-bromo-9H-thioxanthen-9-one were used as starting materials. Mass: [(M+H) + ]:507

[0163] [Preparation Example 6] Synthesis of Core6 [ka]

[0164] Core 6 (41.5 g, 38.9% yield for the three steps) was obtained in the same manner as in Step 1 and Step 2 of Preparative Example 1 and Step 3 of Preparative Example 2, except that 50.0 g (188.6 mmol) of (2-bromophenyl)(phenyl)sulfane and 66.0 g (188.6 mmol) of 2-bromo-10-phenylacridin-9(10H)-one were used as starting materials. Mass: [(M+H) + ]:566

[0165] [Preparation Example 7] Synthesis of Core7 [ka]

[0166] 37.6 g of Core 7 (35.3% yield for the three steps) was obtained in the same manner as in Steps 1, 2, and 3 of Preparative Example 1, except that 50.0 g (188.6 mmol) of (2-bromophenyl)(phenyl)sulfane and 57.6 g (188.6 mmol) of 3-chloro-10-phenylacridin-9(10H)-one were used as starting materials. Mass: [(M+H) + ]:566

[0167] [Preparation Example 8] Synthesis of Core8 [ka]

[0168] 44.0 g of Core 8 (47.6% yield for the three steps) was obtained in the same manner as in Steps 1, 2, and 3 of Preparative Example 1, except that 50.0 g (188.6 mmol) of (2-bromophenyl)(phenyl)sulfane and 43.5 g (188.6 mmol) of 4-chloro-9H-xanthen-9-one were used as starting materials. Mass: [(M+H) + ]:491

[0169] [Preparation Example 9] Synthesis of Core9 [ka]

[0170] 28.3 g of Core 9 (28.2% yield for the three steps) was obtained in the same manner as in Step 1 and Step 2 of Preparative Example 1 and Step 3 of Preparative Example 2, except that 50.0 g (200.7 mmol) of 1-bromo-2-phenoxybenzene and 60.2 g (200.7 mmol) of 7-bromo-9-oxo-9H-xanthene-2-carbonitrile were used as starting materials. Mass: [(M+H) + ]:500

[0171] [Preparation Example 10] Synthesis of Core10 [ka]

[0172] Core 10 (40.1 g, 42.1% yield for the three steps) was obtained in the same manner as in Step 1 and Step 2 of Preparative Example 1 and Step 3 of Preparative Example 2, except that 50.0 g (200.7 mmol) of 1-bromo-2-phenoxybenzene and 55.2 g (200.7 mmol) of 3-bromo-9H-xanthen-9-one were used as starting materials. Mass: [(M+H) + ]:475

[0173] [Preparation Example 11] Synthesis of Core11 [ka]

[0174] Core 11 (27.5 g, 31.2% yield for the three steps) was obtained in the same manner as in Steps 1, 2, and 3 of Preparative Example 1, except that 50.0 g (176.3 mmol) of 1-bromo-2-(4-chlorophenoxy)benzene and 39.0 g (176.3 mmol) of 9-oxo-9H-xanthene-2-carbonitrile were used as starting materials. Mass: [(M+H) + ]:500

[0175] [Preparation Example 12] Synthesis of Core12 [ka]

[0176] Core 12 (41.8 g, 43.9% yield for the three steps) was obtained in the same manner as in Steps 1, 2, and 3 of Preparative Example 1, except that 50.0 g (200.7 mmol) of 1-bromo-2-phenoxybenzene and 46.3 g (200.7 mmol) of 4-chloro-9H-xanthen-9-one were used as starting materials. Mass: [(M+H) + ]:475

[0177] [Synthesis Examples 1 to 21] [Synthesis Example 1] Synthesis of Compound 2 [ka]

[0178] 10.0 g (1 eq, 23.8 mmol) of 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine, 12.3 g (1.05 eq, 25.0 mmol) of Core 1 from [Preparation Example 1], 0.2 g (0.03 eq, 0.7 mmol) of Pd(OAc)2, 3.3 g (3.0 eq, 93.0 mmol) of Cs2CO3, and 0.7 g (0.06 eq, 1.4 mmol) of Xphos were added to 200 ml of toluene, 50 ml of EtOH, and 50 ml of H2O, and the mixture was heated under reflux for 4 hours. After the reaction was complete, the mixture was extracted with dichloromethane, added with MgSO4, and filtered. After removing the solvent from the filtered organic layer, the residue was subjected to column chromatography using dichloromethane and hexane, and then recrystallized from toluene and acetone to obtain 13.9 g of Compound 2 (yield 77.9%). Mass: [(M+H) + ]:749

[0179] [Synthesis Example 2] Synthesis of Compound 5 [ka]

[0180] 10.0 g (1 eq, 25.8 mmol) of 2-(2-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 12.8 g (1.05 eq, 27.0 mmol) of Core 2 (Preparation Example 2), 0.9 g (0.03 eq, 0.8 mmol) of Pd(Pph3), and 10.7 g (3.0 eq, 77.3 mmol) of K2CO3 were added to 200 ml of toluene, 50 ml of EtOH, and 50 ml of HO and heated under reflux for 4 hours. After the reaction was complete, the mixture was extracted with dichloromethane, added with MgSO4, and filtered. After removing the solvent from the filtered organic layer, the mixture was subjected to column chromatography using dichloromethane and hexane, followed by recrystallization with toluene and acetone to obtain 13.9 g (82.5% yield) of compound 5. Mass: [(M+H) + ]:657

[0181] [Synthesis Example 3] Synthesis of Compound 6 [ka]

[0182] The same reagent equivalent ratios and procedures as in [Synthesis Example 2] were used, except that 10.0 g (25.8 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used as the starting material, to obtain 15.0 g (yield 88.9%) of compound 6. Mass: [(M+H) + ]:657

[0183] [Synthesis Example 4] Synthesis of Compound 9 [ka]

[0184] The same equivalent ratios of reagents and procedures as in [Synthesis Example 2] were used, except that 10.0 g (1 eq, 25.8 mmol) of 2-(2-bromophenyl)-4,6-diphenyl-1,3,5-triazine and 14.9 g (1.05 eq, 27.0 mmol) of Core 3 were used as starting materials, to obtain 13.6 g (yield 72.3%) of compound 9. Mass: [(M+H) + ]:732

[0185] [Synthesis Example 5] Synthesis of Compound 16 [ka]

[0186] The same equivalent ratios of reagents and procedures as in Synthesis Example 1 were used, except that 10.0 g (1 eq, 20.2 mmol) of 2-(3′-chloro-[1,1′:3′,1′-terphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine and 10.4 g (1.05 eq, 21.2 mmol) of Core 4 were used as starting materials, to obtain 13.7 g (82.3% yield) of compound 16. Mass: [(M+H) + ]:825

[0187] [Synthesis Example 6] Synthesis of Compound 22 [ka]

[0188] The same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used, except that 10.0 g (1 eq, 23.8 mmol) of 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine and 12.7 g (1.05 eq, 25.0 mmol) of Core 5 were used as starting materials, to obtain 13.2 g (72.5% yield) of compound 22. Mass: [(M+H) + ]:765

[0189] [Synthesis Example 7] Synthesis of Compound 32 [ka]

[0190] The same equivalent ratios of reagents and procedures as in Synthesis Example 1 were used, except that 10.0 g (1 eq, 23.8 mmol) of 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine and 14.1 g (1.05 eq, 25.0 mmol) of Core 6 were used as starting materials, to obtain 12.2 g (yield 62.1%) of compound 32. Mass: [(M+H) + ]:824

[0191] [Synthesis Example 8] Synthesis of Compound 45 [ka]

[0192] The same equivalent ratios of reagents and procedures as in [Synthesis Example 2] were used, except that 10.0 g (1 eq, 25.8 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine and 15.3 g (1.05 eq, 27.0 mmol) of Core 7 were used as starting materials, to obtain 13.5 g of compound 45 (yield 70.3%). Mass: [(M+H) + ]:748

[0193] [Synthesis Example 9] Synthesis of Compound 46 [ka]

[0194] The same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used, except that 10.0 g (1 eq, 23.8 mmol) of 2-(3'-chloro-[1,1'-biphenyl]-2-yl)-4,6-diphenyl-1,3,5-triazine and 14.1 g (1.05 eq, 25.0 mmol) of Core7 were used as starting materials, to obtain 10.8 g (yield 55.1%) of compound 46. Mass: [(M+H) + ]:824

[0195] [Synthesis Example 10] Synthesis of Compound 54 [ka]

[0196] The same equivalent ratios of reagents and procedures as in Synthesis Example 1 were used, except that 10.0 g (1 eq, 23.8 mmol) of 2-(3'-chloro-[1,1'-biphenyl]-2-yl)-4,6-diphenyl-1,3,5-triazine and 12.3 g (1.05 eq, 25.0 mmol) of Core 8 were used as starting materials, to obtain 10.8 g (yield 60.7%) of compound 54. Mass: [(M+H) + ]:749

[0197] [Synthesis Example 11] Synthesis of Compound 71 [ka]

[0198] The same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used, except that 10.0 g (1 eq, 22.5 mmol) of 3'-(4-(3-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-4-carbonitrile and 11.9 g (1.05 eq, 23.6 mmol) of Core 5 were used as starting materials. Compound 71 (12.9 g, yield 73.2%) was obtained using the same procedures as in [Synthesis Example 1]. Mass: [(M+H) + ]:790

[0199] [Synthesis Example 12] Synthesis of Compound 73 [ka]

[0200] The same equivalent ratios of reagents and procedures as in Synthesis Example 1 were used, except that 10.0 g (1 eq, 22.5 mmol) of 4'-(4-(2-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-3-carbonitrile and 11.2 g (1.05 eq, 23.6 mmol) of Core 2 were used as starting materials. Compound 73 (10.9 g, 63.8% yield) was obtained using the same procedures as in Synthesis Example 1. Mass: [(M+H) + ]:758

[0201] [Synthesis Example 13] Synthesis of Compound 74 [ka]

[0202] The same equivalent ratios of reagents and procedures as in Synthesis Example 2 were used, except that 10.0 g (1 eq, 25.8 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine and 13.5 g (1.05 eq, 27.0 mmol) of Core 9 were used as starting materials, to obtain 12.6 g (yield 72.1%) of compound 74. Mass: [(M+H) + ]:682

[0203] [Synthesis Example 14] Synthesis of Compound 76 [ka]

[0204] The same equivalent ratios of reagents and procedures as in Synthesis Example 1 were used, except that 10.0 g (1 eq, 23.8 mmol) of 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine and 12.5 g (1.05 eq, 25.0 mmol) of Core 9 were used as starting materials. Compound 76 (11.4 g, 63.3% yield) was obtained using the same procedures as in Synthesis Example 1. Mass: [(M+H) + ]:758

[0205] [Synthesis Example 15] Synthesis of Compound 77 [ka]

[0206] The same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used, except that 10.0 g (1 eq, 20.2 mmol) of 4-([1,1':2',1''-terphenyl]-4'-yl)-6-(2-chlorophenyl)-2-phenylpyrimidine and 10.1 g (1.05 eq, 21.2 mmol) of Core10 were used as starting materials, to obtain 8.9 g (yield 54.2%) of compound 77. Mass: [(M+H) + ]:808

[0207] [Synthesis Example 16] Synthesis of Compound 78 [ka]

[0208] The starting materials were 4-([1,1':3',1''-terphenyl]-5'-yl)-6-(3-chlorophenyl)-2-phenylpyrimidine (10.0 g, 1 eq, 20.2 mmol) and Core10 (10.1 g, 1.05 eq, 21.2 mmol), but the same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used to obtain 13.5 g of compound 78 (yield 82.9%). Mass: [(M+H) + ]:808

[0209] [Synthesis Example 17] Synthesis of Compound 84 [ka]

[0210] The starting materials were 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (10.0 g, 1 eq, 23.8 mmol) and Core 11 (12.49 g, 1.05 eq, 25.0 mmol), but the same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used to obtain 13.0 g of compound 84 (72.1% yield). Mass: [(M+H) + ]:758

[0211] [Synthesis Example 18] Synthesis of Compound 90 [ka]

[0212] The starting materials were 4'-(4-(3'-chloro-[1,1'-biphenyl]-3-yl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-3-carbonitrile 10.0 g (1 eq, 19.2 mmol) and Core 12 9.6 g (1.05 eq, 20.2 mmol), but the same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used to obtain 7.8 g of compound 90 (yield 48.8%). Mass: [(M+H) + ]:834

[0213] [Synthesis Example 19] Synthesis of Compound 92 [ka]

[0214] The same equivalent ratios of reagents and procedures as in [Synthesis Example 1] were used, except that 10.0 g (1 eq, 20.2 mmol) of 4-([1,1':2',1''-terphenyl]-4'-yl)-6-(2-chlorophenyl)-2-phenylpyrimidine and 10.1 g (1.05 eq, 21.2 mmol) of Core 12 were used as starting materials, to obtain 8.3 g (yield 50.8%) of compound 92. Mass: [(M+H) + ]:808

[0215] [Synthesis Example 20] Synthesis of Compound 93 [ka]

[0216] The same equivalent ratios of reagents and procedures as in Synthesis Example 1 were used, except that 10.0 g (1 eq, 22.5 mmol) of 4'-(4-(3-chlorophenyl)-6-phenyl-1,3,5-triazin-2-yl)-[1,1'-biphenyl]-3-carbonitrile and 11.6 g (1.05 eq, 23.6 mmol) of Core 4 were used as starting materials, to obtain 10.6 g (yield 61.2%) of compound 93. Mass: [(M+H) +]:774

[0217] [Synthesis Example 21] Synthesis of Compound 97 [ka]

[0218] Compound 97 (14.2 g, 86.9% yield) was obtained using the same equivalent ratio of reagents and the same procedure as in Synthesis Example 1, except that 10.0 g (1 eq, 20.2 mmol) of 4-([1,1':2',1''-terphenyl]-4'-yl)-6-(3-chlorophenyl)-2-phenylpyrimidine and 10.1 g (1.05 eq, 21.2 mmol) of Core 2 were used as starting materials. Mass: [(M+H) + ]:808

[0219] [Examples 1 to 7] Preparation of blue fluorescent organic electroluminescence device Each compound synthesized in the above synthesis examples was purified to high purity by sublimation using a conventional method, and then a blue organic electroluminescence device was fabricated as follows.

[0220] First, a glass substrate coated with a 1200 Å thick indium tin oxide (ITO) thin film was ultrasonically cleaned in distilled water. After the distilled water cleaning, the substrate was ultrasonically cleaned with solvents such as isopropyl alcohol, acetone, and methanol, dried, and then transferred to a UV ozone cleaner (Powersonic 405, manufactured by HWASHIN TECH) and cleaned using UV for 5 minutes before being transferred to a vacuum deposition machine.

[0221] On the ITO transparent electrode prepared as described above, the following layers were stacked in this order: HT-1 + 2% HAT-CN (100 Å) / HT-1 (1400 Å) / HT-2 (50 Å) / BH + 2% BD (200 Å) / ET-2 (50 Å) / Compounds 71 ​​to 93 in Table 1 below: LiQ = 1:1 (300 Å) / LiF (10 Å) / Al (1000 Å) to prepare an organic electroluminescence device.

[0222] The structures of the compounds used here, HT-1, HAT-CN, HT-2, BH, BD, ET-1, ET-2, and LiQ, are as follows:

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [Comparative Example 1] Preparation of a blue fluorescent organic electroluminescence device A blue organic electroluminescence device was fabricated in the same manner as in Example 1, except that ET-1 was used instead of Compound 71 as the electron transport layer material.

[0227] [Evaluation example 1] For each of the blue organic electroluminescence devices fabricated in Examples 1 to 7 and Comparative Example 1, a current density of 10 mA / cm 2 The driving voltage, current efficiency, and emission peak were measured at 1000 kJ / s, and the results are shown in Table 1 below.

[0228] [Table 1]

[0229] As shown in Table 1, the blue organic electroluminescent devices of Examples 1 to 7, which used the compounds according to the present invention as electron transport layer materials, exhibited superior performance in terms of driving voltage, emission peak, and current efficiency compared to the blue organic electroluminescent device of Comparative Example 1, which used the conventional compound ET-1, which does not contain a spirobixanthene core, as electron transport layer material.

[0230] [Examples 8 to 21] Production of blue fluorescent organic electroluminescence devices Each compound synthesized in the above synthesis examples was purified to high purity by sublimation using a conventional method, and then a blue organic electroluminescence device was fabricated as follows.

[0231] A glass substrate coated with a 1500 Å thick ITO (indium tin oxide) thin film was ultrasonically cleaned in distilled water. After the distilled water cleaning, the substrate was ultrasonically cleaned with solvents such as isopropyl alcohol, acetone, and methanol, dried, and then transferred to a UV ozone cleaner (Powersonic 405, manufactured by HWASHIN TECH) and cleaned using UV for 5 minutes before being transferred to a vacuum deposition machine.

[0232] On the ITO transparent electrode prepared as described above, the following layers were laminated in this order: HT-1+2% HAT-CN (100 Å) / HT-1 (1400 Å) / HT-2 (50 Å) / BH+2% BD (200 Å) / compounds 2 to 97 (50 Å) in Table 2 below / ET-1:LiQ=1:1 (300 Å) / LiF (10 Å) / Al (1000 Å) to prepare an organic electroluminescence device.

[0233] [Comparative Examples 2 to 5] Production of blue fluorescent organic electroluminescence devices Blue organic electroluminescence devices of Comparative Examples 2 to 5 were fabricated in the same manner as in Example 8, except that ET-2 to ET-5 were deposited to a thickness of 50 Å instead of Compound 2 as the electron transport assisting layer material.

[0234] The structures of the compounds ET-2, ET-3, ET-4, and ET-5 used here are as follows:

[0235] [ka]

[0236] [Evaluation example 2] For the organic electroluminescence devices manufactured in Examples 8 to 21 and Comparative Examples 2 to 5, a current density of 10 mA / cm2 The driving voltage, emission wavelength, and current efficiency were measured at 1000 kJ / s, and the results are shown in Table 2 below.

[0237] [Table 2]

[0238] As shown in Table 2, the blue organic electroluminescent devices of Examples 8 to 21, which contain the compounds of the present invention as electron transport auxiliary layer materials, exhibit superior performance in terms of device current efficiency and driving voltage compared to the blue organic electroluminescent devices of Comparative Examples 2 to 5, which contain, as electron transport auxiliary layer materials, ET-2, which does not contain a spirobixanthene core, and ET-3 to ET-5, which do not contain a linker and have a structure in which the spirobixanthene core and the azine group are directly linked.

Claims

1. A compound represented by the following chemical formula 1: 【Chemistry 1】 In the above Chemical Formula 1, X １ ~X ３ are the same or different, and each independently represents C(R ６ ) or N, with the proviso that X １ ~X ３ at least two of are N, Y １ and Y ２ are the same or different from each other and each independently represent O, S, and NR １１ selected from the group consisting of Ar １ and Ar ２ are the same or different from each other, and each independently represents C １ ~C ４０ alkyl group of C ２ ~C ４０ an alkenyl group of C ２ ~C ４０ an alkynyl group of C ３ ~C ４０ a cycloalkyl group having 3 to 40 ring atoms, a heterocycloalkyl group having 3 to 40 ring atoms, C ６ ~C ６０ an aryl group having 5 to 60 ring atoms; a heteroaryl group having 5 to 60 ring atoms; １ ~C ４０ an alkyloxy group of C ６ ~C ６０ an aryloxy group of C ３ ~C ４０ an alkylsilyl group of C ６ ~C ６０ an arylsilyl group of C １ ~C ４０ alkylboron groups of C ６ ~C ６０ an arylboron group of C ６ ~C ６０ an arylphosphine group of C ６ ~C ６０ an arylphosphine oxide group of the formula C ６ ~C ６０ or which may be joined to any adjacent group to form a fused ring; R １ ~R ６ and R １１ are the same or different and each independently represent hydrogen, deuterium (D), halogen, cyano group, nitro group, C １ ~C ４０ alkyl group of C ２ ~C ４０ an alkenyl group of C ２ ~C ４０ an alkynyl group of C ３ ~C ４０ a cycloalkyl group having 3 to 40 ring atoms, a heterocycloalkyl group having 3 to 40 ring atoms, C ６ ~C ６０ an aryl group having 5 to 60 ring atoms; a heteroaryl group having 5 to 60 ring atoms; １ ~C ４０ an alkyloxy group of C ６ ~C ６０ an aryloxy group of C ３ ~C ４０ an alkylsilyl group of C ６ ~C ６０ an arylsilyl group of C １ ~C ４０ alkylboron groups of C ６ ~C ６０ an arylboron group of C ６ ~C ６０ an arylphosphine group of C ６ ~C ６０ an arylphosphine oxide group of the formula C ６ ~C ６０ or which may be joined to any adjacent group to form a fused ring; L is C ６ ~C １８ and heteroarylene groups having 5 to 18 ring atoms, a is an integer of 1 to 5, and when a is 2 or more, multiple Ls are the same or different; o, p, q, and s are each independently an integer of 0 to 4, and r is an integer of 0 to 3; The arylene group or heteroarylene group of L and the Ar １ ~Ar ２ , R １ ~R ６ , and R １１ The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group, and arylamine group each independently represent a deuterium (D), a halogen, a cyano group, a nitro group, C １ ~C ４０ alkyl group of C ２ ~C ４０ an alkenyl group of C ２ ~C ４０ an alkynyl group of C ３ ~C ４０ a cycloalkyl group having 3 to 40 ring atoms, a heterocycloalkyl group having 3 to 40 ring atoms, C ６ ~C ６０ an aryl group having 5 to 60 ring atoms; a heteroaryl group having 5 to 60 ring atoms; １ ~C ４０ an alkyloxy group of C ６ ~C ６０ an aryloxy group of C １ ~C ４０ an alkylsilyl group of C ６ ~C ６０ an arylsilyl group of C １ ~C ４０ alkylboron groups of C ６ ~C ６０ an arylboron group of C ６ ~C ６０ an arylphosphine group of C ６ ~C ６０ an arylphosphine oxide group of the formula C ６ ~C ６０ In this case, when there are a plurality of the substituents, they may be the same or different.

2. The Y １ and Y ２ The compound according to claim 1, wherein the ring-containing compound is any one selected from the following structural formulas: 【Chemistry 2】 In the above formula, * means a linking site to Chemical Formula 1; R １１ is hydrogen, deuterium (D), C １ ~C ４０ alkyl group of C ６ ~C ６０ and heteroaryl groups having 5 to 60 ring atoms, R １ ~R ４ , o, p, q, and r are defined as in claim 1, respectively.

3. 2. The compound of claim 1, wherein the X-containing moiety is any one selected from the following structural formulas: 【Transformation 3】 In the above formula, * means a linking site to Chemical Formula 1; W is O or S; Ar １ and Ar ２ are defined as in claim 1.

4. Ar １ and Ar ２ are the same or different from each other, and each independently represents C ６ ~C ６０ 2. The compound according to claim 1, wherein the aryl group is selected from the group consisting of aryl groups of the formula (I) and heteroaryl groups having 5 to 60 ring atoms.

5. Ar １ and Ar ２ are each independently any one selected from the following structural formulas: 【Chemistry 4】 【Transformation 5】 In the above formula, * indicates the linking site to Chemical Formula 1.

6. 2. The compound of claim 1, wherein L is a linker selected from the following structural formulas: 【Transformation 6】 In the above formula, * indicates the linking site to Chemical Formula 1.

7. R １ ~R ５ are the same or different and each independently represent hydrogen, deuterium (D), a cyano group, C １ ~C ４０ alkyl group of C ６ ~C ６０ and heteroaryl groups having 5 to 60 ring atoms, or which are bonded to adjacent groups to form a fused ring.

8. The compound represented by Chemical Formula 1 is the compound according to claim 1, which is represented by any one of Chemical Formulas 2 to 10 below: 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 In the above formula, X １ ~X ３ , Ar １ ~Ar ２ , L, R １ ~R ５ , R １１ , o, p, q, r, s, and a are defined as in claim 1.

9. The compound represented by Chemical Formula 1 is the compound according to claim 1, which is represented by any one of Chemical Formulas 11 to 29 below: 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 【Chemistry 32】 【Transformation 33】 【Transformation 34】 In the above formula, Y １ ~Y ２ , Ar １ ~Ar ２ , L, R １ ~R ５ , o, p, q, r, s, and a are defined as in claim 1.

10. The compound represented by Chemical Formula 1 is the compound according to claim 1, which is represented by any one of Chemical Formulas 30 to 37 below: 【Chemistry 35】 【Transformation 36】 【Chemistry 37】 【Transformation 38】 【Chemistry 39】 【Chemistry 40】 【Chemistry 41】 【Chemistry 42】 In the above formula, Ring A is a monocyclic or polycyclic alicyclic ring, a monocyclic or polycyclic heteroalicyclic ring, a monocyclic or polycyclic aromatic ring, or a monocyclic or polycyclic heteroaromatic ring; X １ ~X ３ , Y １ ~Y ２ , Ar １ ~Ar ２ , L, R １ ~R ５ , o, p, q, r, s, and a are defined as in claim 1.

11. The compound represented by Chemical Formula 1 is the compound according to claim 1, which is represented by any one of Chemical Formulas 38 to 40 below: 【Chemistry 43】 【Chemistry 44】 【Chemistry 45】 In the above formula, X １ ~X ３ , Y １ ~Y ２ , Ar １ ~Ar ２ , L, R １ ~R ５ , o, p, q, r, s, and a are defined as in claim 1.

12. The compound represented by Chemical Formula 1 is the compound according to claim 1, which is represented by any one of Chemical Formula 41 and Chemical Formula 42: 【Chemistry 46】 【Chemistry 47】 In the above formula, Z is O or S; X １ ~X ３ , Y １ ~Y ２ , Ar １ ~Ar ２ , R １ ~R ５ , o, p, q, r, s, and a are defined as in claim 1.

13. The compound according to claim 1, wherein the compound represented by Chemical Formula 1 is represented by any one of Chemical Formulas 1 to 100 below. 【Chemistry 48】 【Chemistry 49】 [Transformation 50] 【Chemistry 51】 【Chemistry 52】

14. The compound according to claim 1 , wherein the compound represented by Chemical Formula 1 is a material for a light-emitting layer, an electron-transporting layer, or an electron-transporting auxiliary layer.

15. An organic electroluminescence device comprising an anode, a cathode, and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers comprises the compound according to any one of claims 1 to 14.

16. 16. The organic electroluminescence device according to claim 15, wherein the organic layer containing the compound is selected from the group consisting of a light-emitting layer, a light-emitting auxiliary layer, a life-improving layer, an electron-transporting layer, and an electron-transporting auxiliary layer.

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