Patent Application
20220416174
This application claims priority to and the benefit of Korean Patent Application No. 10-2020-0056177, filed on May 11, 2020, the entire content of which is hereby incorporated by reference.
One or more aspects of embodiments of the present disclosure relate to an organic electroluminescence device and a polycyclic compound for an organic electroluminescence device.
Organic electroluminescence displays are being actively developed as image displays. An organic electroluminescence display differs from a liquid crystal display, and is a so-called self-luminescent display, in which holes and electrons respectively injected from a first electrode and a second electrode recombine in an emission layer, and a light-emitting material including an organic compound in the emission layer emits light to attain display.
In the application of organic electroluminescence devices (or organic electroluminescence display(s)) to a display device, a decreased driving voltage, and increased emission efficiency and/or lifespan of the organic electroluminescence devices are desired, and materials for an organic electroluminescence device stably attaining these characteristics are desired.
One or more aspects of embodiments of the present disclosure are directed toward an organic electroluminescence device and a polycyclic compound for an organic electroluminescence device, and for example, an organic electroluminescence device with high efficiency and a polycyclic compound included in the hole transport region of the organic electroluminescence device.
One or more example embodiments of the present disclosure provide an organic electroluminescence device including: a first electrode; a hole transport region provided on the first electrode; an emission layer provided on the hole transport region; an electron transport region provided on the emission layer; and a second electrode provided on the electron transport region, wherein the hole transport region includes a polycyclic compound represented by Formula 1:
In Formula 1,
X may be O or S,
any one among A1 to A10 may be represented by Formula 2-1, and the remainder may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring:
In Formula 2-1, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 carbon atoms for forming a ring or a substituted or unsubstituted heteroarylene group of 2 to 30 carbon atoms for forming a ring, “m” and “n” may each independently be an integer of 0 to 2, Ar1-1 and Ar2-1 may each independently be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring or represented by Formula 3-1 or Formula 3-2, where at least one of Ar1-1 and Ar2-1 may be represented by Formula 3-1 or Formula 3-2. In a case where X is O, and any one of A2, A3, A8 and A10 is represented by Formula 2-1, Ar1-1 and Ar2-1 may each independently be represented by Formula 3-1 or Formula 3-2:
In Formula 3-1 and Formula 3-2, R1 to R5 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms for forming a ring, “a” may be an integer of 0 to 3, “b”, “c”, and “e” may each independently be an integer of 0 to 4, and “d” may be an integer of 0 to 2, where c+d+e is an integer of 9 or less.
In an embodiment, any one of A1 to A10 in Formula 1 may be represented by Formula 2-2, and the remainder may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring:
In Formula 2-2, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group of 2 to 30 carbon atoms for forming a ring, “m” and “n” may each independently be an integer of 0 to 2, and Ar1-2 and Ar2-2 may each independently be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring or represented by Formula 3-3 or Formula 3-4, where at least one among Ar1-2 and Ar2-2 is represented by Formula 3-3 or Formula 3-4:
In Formula 3-3 and Formula 3-4, Y and Z may each independently be a direct linkage, O, or S, where a case in which both Y and Z are direct linkages is excluded (e.g., Y and Z are not simultaneously a direct linkage), R6 to R9 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms for forming a ring, “f” may be an integer of 0 to 3, “g” to “i” may each independently be an integer of 0 to 4, and Ar3 to Ar5 may each independently be a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring.
In an embodiment, any one among A1 to A10 in Formula 1 may be represented by Formula 2-3, and the remainder may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring:
In Formula 2-3, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 carbon atoms for forming a ring or a substituted or unsubstituted heteroarylene group of 2 to 30 carbon atoms for forming a ring, “m” and “n” may each independently be an integer of 0 to 2, and Ar1-3 and Ar2-3 may each independently be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring or represented by Formula 3-5 or Formula 3-6, where at least one among Ar1-3 and Ar2-3 is represented by Formula 3-5 or Formula 3-6:
In Formula 3-5 and Formula 3-6, R10 and R11 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms for forming a ring; Ar6 may be a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, “j” and “k” may each independently be an integer of 0 to 4, and “p” is an integer of 0 to 3.
In an embodiment, Formula 2-1 may be represented by Formula 4-1 or Formula 4-2:
In Formula 4-1 and Formula 4-2, Ar2-1 may be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring, L1, L2, “m” and “n” may each independently be the same as defined in Formula 2-1, and R1 to R5, and “a” to “d” may each independently be the same as defined in Formula 3-1 and Formula 3-2.
In an embodiment, Formula 2-2 may be represented by Formula 5-1 or Formula 5-2:
In Formula 5-1 and Formula 5-2, Ar2-2 may be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring; L1, L2, “m” and “n” may each independently be the same as defined in Formula 2-2; and Y, Z, R6 to R9, “f” to “i”, and Ar3 to Ar5 may each independently be the same as defined in Formula 3-3 and Formula 3-4.
In an embodiment, Formula 2-3 may be represented by Formula 6-1 or Formula 6-2:
In Formula 6-1 and Formula 6-2, Ar2-3 may be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring; L1, L2, “m” and “n” may each independently be the same as defined in Formula 2-3; and R10 and R11, Ar6, “j”, “k”, and “p” may each independently be the same as defined in Formula 3-5 and Formula 3-6.
In an embodiment, any one among A1 to A6 in Formula 1 may be represented by Formula 2-1.
In an embodiment, A7 or A10 in Formula 1 may be represented by Formula 2-1.
In an embodiment, any one among A1 to A6 in Formula 1 may be represented by Formula 2-2.
In an embodiment, any one among A7 to A10 in Formula 1 may be represented by Formula 2-2.
In an embodiment, any one among A1 to A6 in Formula 1 may be represented by Formula 2-3.
In an embodiment, any one among A7 to A10 in Formula 1 may be represented by Formula 2-3.
In an embodiment, the hole transport region may include a hole injection layer disposed on the first electrode, and a hole transport layer disposed on the hole injection layer, where the hole transport layer may include the polycyclic compound represented by Formula 1.
In an embodiment, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthyl group.
In an embodiment, L2 may be a direct linkage or a substituted or unsubstituted phenyl group, “n” may be 1, and Ar2-1 to Ar2-3 may each independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted phenanthrene group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group, where a case in which L2 and any one among Ar2-1 to Ar2-3 (e.g., L2 and Ar2-1, L2 and Ar2-2, or L2 and Ar2-3) are simultaneously phenyl groups (e.g., at the same time) may be excluded.
In an embodiment, the polycyclic compound represented by Formula 1 may be at least one selected from the compounds represented in Compound Group 1 to Compound Group 6.
One or more example embodiments of the present disclosure provide a polycyclic compound represented by Formula 1.
The accompanying drawings are included to provide a further understanding of the present disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate example embodiments of the present disclosure and, together with the description, serve to explain principles of the present disclosure. In the drawings:
The present disclosure may have various modifications and may be embodied in different forms, and example embodiments will be explained in more detail with reference to the accompanying drawings. The present disclosure may, however, be embodied in different forms and should not be construed as being limited to the embodiments set forth herein. Rather, all modifications, equivalents, and substituents that are within the spirit and technical scope of the present disclosure should be included in the present disclosure.
It will be understood that when an element (or region, layer, part, etc.) is referred to as being “on”, “connected to” or “coupled to” another element, it can be directly on, connected or coupled to the other element, or one or more intervening elements may be present. When an element is referred to as being “directly on,” “directly connected to,” or “directly coupled to” another element, there are no intervening elements present.
Like reference numerals refer to like elements throughout, and duplicative descriptions thereof may not be provided. In the drawings, thicknesses, ratios, and dimensions of constituent elements may be exaggerated for effective explanation of technical contents.
As used herein, expressions such as “at least one of,” “one of,” and “selected from,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list. The term “and/or” includes any and all combinations of one or more of the associated listed items. Further, the use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure”.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Thus, a first element could be alternatively termed a second element without departing from the teachings of the present disclosure. Similarly, a second element could be alternatively termed a first element. As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In addition, the terms “below”, “beneath”, “on” and “above” are used for explaining spatial relationships between elements shown in the drawings. The terms are relative concepts, and are selected and to be interpreted based on the orientations shown in the drawing.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
It will be further understood that the terms “includes,” “including,” “comprises,” and/or “comprising,” when used in this specification, specify the presence of stated features, numerals, steps, operations, elements, parts, or combinations thereof, but do not preclude the presence or addition of one or more other features, numerals, steps, operations, elements, parts, or combinations thereof.
Hereinafter, the organic electroluminescence device according to an embodiment of the present disclosure will be explained with reference to the attached drawings.
In some embodiments, the organic electroluminescence device 10 of an embodiment further includes a plurality of functional layers between the first electrode EL1 and the second electrode EL2 in addition to the emission layer EML. The plurality of functional layers may include a hole transport region HTR and an electron transport region ETR. For example, the organic electroluminescence device 10 of an embodiment may include a first electrode EL1, a hole transport region HTR, an emission layer EML, an electron transport region ETR, and a second electrode, stacked one by one. In some embodiments, the organic electroluminescence device 10 of an embodiment may include a capping layer CPL disposed on the second electrode EL2.
The organic electroluminescence device 10 of an embodiment includes a polycyclic compound of an embodiment, which will be explained later, in the emission layer EML disposed between the first electrode EL1 and the second electrode EL2. However, embodiments of the present disclosure are not limited thereto, and the organic electroluminescence device 10 of an embodiment may include a polycyclic compound according to an embodiment in the hole transport region HTR or the electron transport region ETR (which are among the plurality of functional layers disposed between the first electrode EL1 and the second electrode EL2), or in the capping layer CPL disposed on the second electrode EL2 in addition to the emission layer EML.
Compared with
The first electrode EL1 has conductivity (e.g., may be conductive). The first electrode EL1 may be formed using a metal alloy or a conductive compound. The first electrode EL1 may be a pixel electrode or an anode. The first electrode EL1 may be a transmissive electrode, a transflective electrode, or a reflective electrode. When the first electrode EL1 is a transmissive electrode, the first electrode EL1 may be formed using a transparent metal oxide (such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), and/or indium tin zinc oxide (ITZO)). When the first electrode EL1 is a transflective electrode or a reflective electrode, the first electrode EL1 may include silver (Ag), magnesium (Mg), copper (Cu), aluminum (Al), platinum (Pt), palladium (Pd), gold (Au), nickel (Ni), neodymium (Nd), iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca), LiF/Ca, LiF/Al, molybdenum (Mo), titanium (Ti), a compound thereof, or a mixture thereof (for example, a mixture of Ag and Mg). In some embodiments, the first electrode EL1 may have a structure including a plurality of layers, including a reflective layer or a transflective layer formed using the above materials, and a transmissive conductive layer formed using ITO, IZO, ZnO, and/or ITZO. For example, the first electrode EL1 may include a three-layer structure of ITO/Ag/ITO. However, embodiments of the present disclosure are not limited thereto. The thickness of the first electrode EL1 may be about 1,000 Å to about 10,000 Å, for example, about 1,000 Å to about 3,000 Å.
The hole transport region HTR is provided on the first electrode EL1. The hole transport region HTR may include at least one of a hole injection layer HIL, a hole transport layer HTL, a hole buffer layer, or an electron blocking layer EBL.
The hole transport region HTR may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multilayer structure including a plurality of layers formed using a plurality of different materials.
For example, the hole transport region HTR may have the structure of a single layer of a hole injection layer HIL or a hole transport layer HTL, or may have the structure of a single layer formed using a hole injection material and a hole transport material. In some embodiments, the hole transport region HTR may have the structure of a single layer formed using a plurality of different materials, or a structure stacked from the first electrode EL1 of hole injection layer HIL/hole transport layer HTL, hole injection layer HIL/hole transport layer HTL/hole buffer layer, hole injection layer HIL/hole buffer layer, hole transport layer HTL/hole buffer layer, or hole injection layer HIL/hole transport layer HTL/electron blocking layer EBL, without limitation.
The hole transport region HTR of the organic electroluminescence device 10 of an embodiment includes the polycyclic compound according to an embodiment of the present disclosure.
In the description, the term “substituted or unsubstituted” refers to a state of being unsubstituted, or substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a silyl group, an oxy group, a thio group, a sulfinyl group, a sulfonyl group, a carbonyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkenyl group, an alkoxy group, a hydrocarbon ring group, an aryl group, and a heterocyclic group. In addition, each of the exemplified substituents may be further substituted or unsubstituted. Further, a biphenyl group may be interpreted as a named aryl group, or as a phenyl group substituted with a phenyl group.
In the description, non-limiting examples of the halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, and/or an iodine atom.
In the description, the term “alkyl group” may refer to a linear, branched or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Examples of the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, i-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, t-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldocecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc., without limitation.
In the description, the term “alkenyl group” may refer to a hydrocarbon group including one or more carbon-carbon double bonds in the middle or at the terminal end of an alkyl group of 2 or more carbon atoms. The alkenyl group may include a linear chain or a branched chain. The carbon number of the alkenyl group is not specifically limited, but may be 2 to 30, 2 to 20, or 2 to 10. Examples of the alkenyl group include a vinyl group, a 1-butenyl group, a 1-pentenyl group, a 1,3-butadienyl aryl group, a styrenyl group, a styrylvinyl group, etc., without limitation.
In the description, the term “alkynyl group” may refer to a hydrocarbon group including one or more carbon-carbon triple bonds in the middle or at the terminal end of an alkyl group of 2 or more carbon atoms. The alkynyl group may include a linear chain or a branched chain. The carbon number of the alkynyl group is not specifically limited, but may be 2 to 30, 2 to 20, or 2 to 10. Examples of the alkynyl group include an ethynyl group, a propynyl group, etc., without limitation.
In the description, the term “hydrocarbon ring group” may refer to an optional functional group or substituent derived from an aliphatic hydrocarbon ring, or an optional functional group or substituent derived from an aromatic hydrocarbon ring. The carbon number for forming a ring of the hydrocarbon ring group may be 5 to 60, 5 to 30, or 5 to 20.
In the description, the term “aryl group” may refer to an optional functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The carbon number for forming a ring of the aryl group may be 6 to 30, 6 to 20, or 6 to 15. Examples of the aryl group may include phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, quaterphenyl, quinquephenyl, sexiphenyl, triphenylenyl, pyrenyl, benzofluoranthenyl, chrysenyl, etc., without limitation.
In the description, the fluorenyl group may be substituted, and two substituents (e.g., at the 9H position) may be combined with each other to form a spiro structure. Examples of a substituted fluorenyl group are as follows. However, embodiments of the present disclosure are not limited thereto:
In the description, the term “heterocyclic group” may refer to an optional functional group or substituent derived from a ring including one or more among B, O, N, P, Si and S as heteroatoms. The heterocyclic group may include an aliphatic heterocyclic group and an aromatic heterocyclic group. The aromatic heterocyclic group may be a heteroaryl group. The aliphatic heterocyclic group and the aromatic heterocyclic group may be monocycles or polycycles.
In the description, the heterocyclic group may include one or more among B, O, N, P, Si and S as heteroatoms. When the heterocyclic group includes two or more heteroatoms, the two or more heteroatoms may be the same or different. The heterocyclic group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group, and has a concept including a heteroaryl group. The carbon number for forming a ring of the heteroaryl group may be 2 to 30, 2 to 20, or 2 to 10.
In the description, the aliphatic heterocyclic group may include one or more among B, O, N, P, Si and S as heteroatoms. The carbon number for forming a ring of the aliphatic heterocyclic group may be 2 to 30, 2 to 20, or 2 to 10. Examples of the aliphatic heterocyclic group include an oxirane group, a thiirane group, a pyrrolidine group, a piperidine group, a tetrahydrofuran group, a tetrahydrothiophene group, a thiane group, a tetrahydropyran group, a 1,4-dioxane group, etc., without limitation.
In the description, the heteroaryl group may include one or more among B, O, N, P, Si and S as heteroatoms. When the heteroaryl group includes two or more heteroatoms, the two or more heteroatoms may be the same or different. The heteroaryl group may be a monocyclic heteroaryl group or polycyclic heteroaryl group. The carbon number for forming a ring of the heteroaryl group may be 2 to 30, 2 to 20, or 2 to 10. Examples of the heteroaryl group may include thiophene, furan, pyrrole, imidazole, triazole, pyridine, bipyridine, pyrimidine, triazine, triazole, acridyl, pyridazine, pyrazinyl, quinoline, quinazoline, quinoxaline, phenoxazine, phthalazine, pyrido pyrimidine, pyrido pyrazine, pyrazino pyrazine, isoquinoline, indole, carbazole, N-arylcarbazole, N-heteroarylcarbazole, N-alkylcarbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophene, dibenzothiophene, thienothiophene, benzofuran, phenanthroline, thiazole, isooxazole, oxazole, oxadiazole, thiadiazole, phenothiazine, dibenzosilole, dibenzofuran, etc., without limitation.
In the description, the carbon number of the amine group is not specifically limited, but may be 1 to 30. The amine group may include an alkyl amine group, an aryl amine group, or a heteroaryl amine group. Examples of the amine group include a methylamine group, a dimethylamine group, a phenylamine group, a diphenylamine group, a naphthylamine group, a 9-methyl-anthracenylamine group, a triphenylamine group, etc., without limitation.
In the description, the explanation on the aryl group is applied to an arylene group except that the arylene group is a divalent group.
In the description, the explanation on the heteroaryl group is applied to a heteroarylene group except that the arylene group is a divalent group.
In the description, “” and “
” indicate positions of connection (e.g., to other groups, moieties, etc.).
The polycyclic compound according to an embodiment of the present disclosure is represented by Formula 1:
In Formula 1, X may be O or S.
In Formula 1, any one among A1 to A10 may be represented by Formula 2-1, and the remainder may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring:
In Formula 2-1, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group of 2 to 30 carbon atoms for forming a ring.
In Formula 2-1, “m” and “n” are each independently an integer of 0 to 2, where when “m” is 2 or more, a plurality of L1 groups may be the same or different from each other, and when “n” is 2 or more, a plurality of L2 groups may be the same or different from each other.
In Formula 2-1, Ar1-1 and Ar2-1 may each independently be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring, or may be represented by Formula 3-1 or Formula 3-2, where at least one among Ar1-1 and Ar2-1 is represented by Formula 3-1 or Formula 3-2.
When X is O in Formula 1, and any one among A2, A3, A8 and A10 is represented by Formula 2-1, Ar1-1 and Ar2-1 may each independently be represented by Formula 3-1 or Formula 3-2.
In Formula 2-1, “” indicates a position connected with Formula 1.
In Formula 3-1 and Formula 3-2, R1 to R5 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms for forming a ring.
In Formula 3-1, “a” may be an integer of 0 to 3, and when “a” is 2 or more, a plurality of R1 groups may be the same or different from each other.
In Formula 3-1, “b” may be an integer of 0 to 4, and when “b” is 2 or more, a plurality of R2 groups may be the same or different from each other.
In Formula 3-2, “c” and “e” may each independently be an integer of 0 to 4, and when “c” is 2 or more, a plurality of R3 groups may be the same or different from each other, and when “e” is 2 or more, a plurality of R5 groups may be the same or different from each other.
In Formula 3-2, “d” may be an integer of 0 to 2, and when “d” is 2, a plurality of R4 groups may be the same or different from each other.
In Formula 3-2, c+d+e may be an integer of 9 or less.
In Formula 3-1 and Formula 3-2, “” indicates a position connected with Formula 2-1.
In an embodiment, L1 and L2 of Formula 2-1 may each independently be a direct linkage, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthyl group.
In an embodiment, L2 of Formula 2-1 may be a direct linkage or a substituted or unsubstituted phenyl group, and when “n” is 1, each Ar2-1 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group. However, a case in which L2 and Ar2-1 are phenyl groups at the same time is excluded.
In an embodiment, any one among A1 to A6 in Formula 1 may be represented by Formula 2-1.
In an embodiment, A7 or A10 in Formula 1 may be represented by Formula 2-1.
In an embodiment, any one among A1 to A10 in the polycyclic compound represented by Formula 1 may be represented by Formula 2-2, and the remainder may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring:
In Formula 2-2, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group of 2 to 30 carbon atoms for forming a ring.
In Formula 2-2, “m” and “n” may each independently be an integer of 0 to 2, and when “m” is 2 or more, a plurality of L1 groups may be the same or different from each other, and when “n” is 2 or more, a plurality of L2 groups may be the same or different from each other.
In Formula 2-2, Ar1-2 and Ar2-2 may each independently be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring, or may be represented by Formula 3-3 or Formula 3-4, where at least one among Ar1-2 and Ar2-2 is represented by Formula 3-3 or Formula 3-4.
In Formula 2-2, “” indicates a position connected with Formula 1.
In Formula 3-3, Y and Z may each independently be a direct linkage, O, or S, where a case in which both Y and Z are direct linkages is excluded.
In Formula 3-3, R6 to R9 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms for forming a ring.
In Formula 3-3, “f” may be an integer of 0 to 3, and when “f” is 2 or more, a plurality of R6 groups may be the same or different from each other.
In Formula 3-3, “g” to “i” may each independently be an integer of 0 to 4, and when “g” is 2 or more, a plurality of R7 groups may be the same or different from each other, when “h” is 2 or more, a plurality of R8 groups may be the same or different from each other, and when “i” is 2 or more, a plurality of R9 groups may be the same or different from each other.
In Formula 3-4, Ar3 to Ar5 may each independently be a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring.
In Formula 3-3 and Formula 3-4, “” indicates a position connected with Formula 2-2.
In an embodiment, L1 and L2 in Formula 2-2 may be a direct linkage, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthyl group.
In an embodiment, L2 in Formula 2-2 is a direct linkage or a substituted or unsubstituted phenyl group, and when “n” is 1, each Ar2-2 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group. However, a case in which L2 and Ar2-2 are phenyl groups at the same time is excluded.
In an embodiment, any one among A1 to A6 in Formula 1 may be represented by Formula 2-2.
In an embodiment, any one among A7 to A10 in Formula 1 may be represented by Formula 2-2.
In an embodiment, any one among A1 to A10 in Formula 1 may be represented by Formula 2-3, and the remainder may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring:
In Formula 2-3, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group of 2 to 30 carbon atoms for forming a ring.
In Formula 2-3, “m” and “n” may each independently be an integer of 0 to 2, and when “m” is 2 or more, a plurality of L1 groups may be the same or different from each other, and when “n” is 2 or more, a plurality of L2 may be the same or different from each other.
In Formula 2-3, Ar1-3 and Ar2-3 may each independently be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring, or may be represented by Formula 3-5 or Formula 3-6 below, where at least one among Ar1-3 and Ar2-3 is represented by Formula 3-5 or Formula 3-6.
In Formula 2-3, “” indicates a position connected with Formula 1.
In Formula 3-5 and Formula 3-6, R10 and R11 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms for forming a ring.
In Formula 3-5 and Formula 3-6, “j” and “k” may each independently be an integer of 0 to 4, and when “j” is 2 or more, a plurality of R10 groups may be the same or different from each other, and when “k” is 2 or more, a plurality of R1 groups may be the same or different from each other.
In Formula 3-6, “p” may be an integer of 0 to 3, and when “p” is 2 or more, a plurality of R10 groups may be the same or different from each other.
In Formula 3-6, Ar6 may be a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring.
In Formula 3-5 and Formula 3-6, “” indicates a position connected with Formula 2-3.
In an embodiment, L1 and L2 in Formula 2-3 may each independently be a direct linkage, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthyl group.
In an embodiment, L2 of Formula 2-3 is a direct linkage or a substituted or unsubstituted phenyl group, and when “n” is 1, each Ar2-3 may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted fluorenyl group. However, a case in which L2 and Ar2-3 are phenyl groups at the same time is excluded.
In an embodiment, any one among A1 to A6 in Formula 1 may be represented by Formula 2-3.
In an embodiment, any one among A7 to A10 in Formula 1 may be represented by Formula 2-3.
In the polycyclic compound of the present disclosure, the polycyclic compound represented by Formula 1 makes a direct linkage (e.g., is directly linked) with the amine group represented by Formula 2-1 to Formula 2-3 without a linker therebetween.
In an embodiment, Formula 2-1 may be represented by Formula 4-1 or Formula 4-2:
In Formula 4-1 and Formula 4-2, Ar2-1 may be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring.
In Formula 4-1 and Formula 4-2, L1, L2, “m” and “n” may be the same as defined in Formula 2-1, and R1 to R5, and “a” to “e” may be the same as defined in Formula 3-1 and Formula 3-2.
In Formula 4-1 and Formula 4-2, “” indicates a position connected with Formula 1.
In an embodiment, Formula 2-2 may be represented by Formula 5-1 or Formula 5-2:
In Formula 5-1 and Formula 5-2, Ar2-2 may be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring.
In Formula 5-1 and Formula 5-2, L1, L2, “m” and “n” may each independently be the same as defined in Formula 2-2, and Y, Z, R6 to R9, “f” to “i”, and Ar3 to Ar5 may each independently be the same as defined in Formula 3-3 and Formula 3-4.
In Formula 5-1 and Formula 5-2, “” indicates a position connected with Formula 1.
In an embodiment, Formula 2-3 may be represented by Formula 6-1 or Formula 6-2:
In Formula 6-1 and Formula 6-2, Ar2-3 may be a substituted or unsubstituted aryl group of 10 to 40 carbon atoms for forming a ring.
In Formula 6-1 and Formula 6-2, L1, L2, “m” and “n” may each independently be the same as defined in Formula 2-3, and R10 and R11, Ar6, “j”, “k”, and “p” may each independently be the same as defined in Formula 3-5 and Formula 3-6.
In Formula 6-1 and Formula 6-2, “” indicates a position connected with Formula 1.
The polycyclic compound represented by Formula 1 according to an embodiment of the present disclosure may be at least one selected from the compounds represented in Compound Group 1 to Compound Group 6:
Referring to
As described above, the hole transport region HTR includes the polycyclic compound according to an embodiment of the present disclosure. For example, the hole transport region HTR includes the polycyclic compound represented by Formula 1.
When the hole transport region HTR has a multilayer structure having a plurality of layers, any one layer among the plurality of layers may include the polycyclic compound represented by Formula 1. For example, the hole transport region HTR may include a hole injection layer HIL disposed on the first electrode EL1 and a hole transport layer HTL disposed on the hole injection layer HIL, and the hole transport layer HTL may include the polycyclic compound represented by Formula 1. However, embodiments of the present disclosure are not limited thereto, and for example, the hole injection layer HIL may include the polycyclic compound represented by Formula 1.
The hole transport region HTR may include at least one structure of the polycyclic compound represented by Formula 1. For example, the hole transport region HTR may include at least one selected among the compounds represented in the Compound Group 1 to Compound Group 6 above.
The hole transport region HTR may be formed using any suitable method (such as a vacuum deposition method, a spin coating method, a cast method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and/or a laser induced thermal imaging (LITI) method).
However, the hole transport region may further include the materials below in each layer.
The hole injection layer HIL may include, for example, a phthalocyanine compound (such as copper phthalocyanine), N,N′-diphenyl-N,N′-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-phenyl-4,4′-diamine (DNTPD), 4,4′,4″-[tris(3-methylphenyl)phenylamino] triphenylamine (m-MTDATA), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4′,4″-tris{N,-2-naphthyl)-N-phenylamino}-triphenylamine (2-TNATA), poly(3,4-ethylene dioxythiophene)/poly(4-styrene sulfonate) (PEDOT/PSS), polyaniline/dodecylbenzene sulfonic acid (PANI/DBSA), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrene sulfonate) (PANI/PSS), N,N′-di(1-naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPD), triphenylamine-containing polyether ketone (TPAPEK), 4-isopropyl-4′-methyldiphenyliodonium [tetrakis(pentafluorophenyl)borate], and dipyrazino[2,3-f:2′,3′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN).
The hole transport layer HTL may include any suitable hole transport material available in the art, for example, carbazole derivatives (such as N-phenyl carbazole and/or polyvinyl carbazole), fluorene-based derivatives, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD), triphenylamine-based derivatives (such as 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA)), N,N′-di(1-naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPD), 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine (TAPC), 4,4′-bis[N,N′-(3-tolyl)amino]-3,3′-dimethylbiphenyl (HMTPD), 1,3-bis(N-carbazolyl)benzene (mCP), etc.
The electron blocking layer EBL may include, for example, carbazole derivatives (such as N-phenyl carbazole and/or polyvinyl carbazole), fluorene-based derivatives, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD), triphenylamine-based derivatives (such as 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA)), N,N′-di(1-naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPD), 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine (TAPC), 4,4′-bis[N,N′-(3-tolyl)amino]-3,3′-dimethylbiphenyl (HMTPD), mCP, etc.
The thickness of the hole transport region HTR may be about 50 Å to about 15,000 Å, for example, about 100 Å to about 5,000 Å. The thickness of the hole injection region HIL may be, for example, about 30 Å to about 1,000 Å, and the thickness of the hole transport layer HTL may be about 30 Å to about 1,000 Å. For example, the thickness of the electron blocking layer EBL may be about 10 Å to about 1,000 Å. When the thicknesses of the hole transport region HTR, the hole injection layer HIL, the hole transport layer HTL and the electron blocking layer EBL satisfy the above-described ranges, satisfactory hole transport properties may be achieved without substantial increase of a driving voltage.
The hole transport region HTR may further include a charge generating material in addition to the above-described materials to increase conductivity. The charge generating material may be dispersed substantially uniformly or non-uniformly in the hole transport region HTR. The charge generating material may be, for example, a p-dopant. The p-dopant may be one of quinone derivatives, metal oxides, or cyano group-containing compounds, without limitation. For example, non-limiting examples of the p-dopant may include quinone derivatives (such as tetracyanoquinodimethane (TCNQ) and/or 2,3,5,6-tetrafluoro-7,7′,8,8′-tetracyanoquinodimethane (F4-TCNQ)), metal halides (such as MgF2, CuI, and/or RbI), metal oxides (such as tungsten oxide and/or molybdenum oxide), without limitation.
As described above, the hole transport region HTR may further include at least one of a hole butter layer or an electron blocking layer EBL. The hole buffer layer may compensate for an optical resonance distance of light emitted from an emission layer EML, and may increase the light emission efficiency of the device. Materials that may be included in a hole transport region HTR may also be used as materials in a hole buffer layer. The electron blocking layer EBL may prevent or reduce electron injection from the electron transport region ETR to the hole transport region HTR.
The emission layer EML is provided on the hole transport region HTR. The emission layer EML may have a thickness of, for example, about 100 Å to about 1,000 Å or about 100 Å to about 600 Å. The emission layer EML may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multilayer structure having a plurality of layers formed using a plurality of different materials.
As the material of the emission layer EML, any suitable luminescent materials may be used, for example, fluoranthene derivatives, pyrene derivatives, arylacetylene derivatives, anthracene derivatives, fluorene derivatives, perylene derivatives, and chrysene derivatives. In some embodiments, pyrene derivatives, perylene derivatives, and anthracene derivatives may be included. For example, as the host material of the emission layer EML, anthracene derivatives represented by Formula 10 below may be used.
In Formula 10, W1 to W4 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group of 2 to 30 carbon atoms for forming a ring, and/or may be combined with an adjacent group to form a ring. m1 and m2 may each independently be an integer of 0 to 4, and m3 and m4 may each independently be an integer of 0 to 5.
When m1 is 1, W1 may not be a hydrogen atom; when m2 is 1, W2 may not be a hydrogen atom; when m3 is 1, W3 may not be a hydrogen atom; and when m4 is 1, W4 may not be a hydrogen atom.
When m1 is 2 or more, a plurality of W1 groups are the same or different; when m2 is 2 or more, a plurality of W2 groups are the same or different; when m3 is 2 or more, a plurality of W4 groups are the same or different; and when m4 is 2 or more, a plurality of W4 groups are the same or different.
The compound represented by Formula 10 may include, for example, the compounds represented by the structures below. However, the compound represented by Formula 10 is not limited thereto:
The emission layer EML may include a dopant, and the dopant may include any suitable dopant material. For example, the dopant may include at least one among styryl derivatives (for example, 1,4-bis[2-(3-N-ethylcarbazolyl)vinyl]benzene (BCzVB), 4-(di-p-tolylamino)-4″-[(di-p-tolylamino)styryl]stilbene (DPAVB), and N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine (N-BDAVBi)), perylene and derivatives thereof (for example, 2,5,8,11-tetra-t-butylperylene (TBP)), and pyrene and derivatives thereof (for example, 1,1-dipyrene, 1,4-dipyrenylbenzene, 1,4-bis(N,N-diphenylamino)pyrene), 1,6-bis(N,N-diphenylamino)pyrene), 2,5,8,11-tetra-t-butylperylene (TBP), and 1,3,5-tris(1-phenyl-1H-benz[d]imidazole-2-yl)benzene)), without limitation.
The emission layer EML may include a host material. For example, the emission layer EML may include as a host material, at least one among tris(8-hydroxyquinolino)aluminum (Alq3), bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), 4,4′-bis(N-carbazol-9-yl)biphenyl (CBP), 1,3-bis(carbazol-9-yl)benzene (mCP), 2,8-bis(diphenylphosphoryl)dibenzo[b,d]furan (PPF), 4,4′,4″-tris(carbazol-9-yl)-triphenylamine (TCTA), poly(N-vinylcarbazole) (PVK), 9,10-di(naphthalene-2-yl)anthracene (ADN), 3-tert-butyl-9,10-di(naphth-2-yl)anthracene (TBADN), distyrylarylene (DSA), 4,4′-bis(9-carbazolyl)-2,2′-dimethyl-biphenyl (CDBP), 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN), hexaphenyl cyclotriphosphazene (CP1), 1,4-bis(triphenylsilyl)benzene (UGH-2), hexaphenylcyclotrisiloxane (DPSiO3), octaphenylcyclotetrasiloxane (DPSiO4), 2,8-bis(diphenylphosphoryl)dibenzofuran (PPF), and 1,3,5-tris(1-phenyl-1H-benz[d]imidazol-2-yl)benzene (TPBi), without limitation.
When the emission layer EML is to emit red light, the emission layer EML may further include, for example, a fluorescence material including tris(dibenzoylmethanato)phenanthroline europium (PBD:Eu(DBM)3(Phen)) or perylene. When the emission layer EML is to emit red light, the dopant included in the emission layer EML may be selected from, for example, a metal complex or an organometallic complex (such as bis(1-phenylisoquinoline)acetylacetonate iridium (PIQIr(acac)), bis(1-phenylquinoline)acetylacetonate iridium (PQIr(acac)), tris(1-phenylquinoline)iridium (PQIr), and/or octaethylporphyrin platinum (PtOEP)), rubrene and derivatives thereof, and 4-dicyanomethylene-2-(p-dimethylaminostyryl)-6-methyl-4H-pyran (DCM) and derivatives thereof.
When the emission layer EML is to emit green light, the emission layer EML may further include, for example, a fluorescence material including tris(8-hydroxyquinolino)aluminum (Alq3). When the emission layer EML is to emit green light, the dopant included in the emission layer EML may be selected from, for example, a metal complex or an organometallic complex (such as fac-tris(2-phenylpyridine)iridium (Ir(ppy)3)), and coumarin and derivatives thereof.
When the emission layer EML is to emit blue light, the emission layer EML may further include a fluorescence material including any one selected from the group consisting of spiro-DPVBi, spiro-6P, distyryl-benzene (DSB), distyryl-arylene (DSA), a polyfluorene (PFO)-based polymer, and a poly(p-phenylene vinylene (PPV)-based polymer. When the emission layer EML is to emit blue light, the dopant included in the emission layer EML may be selected from, for example, a metal complex or an organometallic complex (such as (4,6-F2ppy)2Irpic), and perylene and derivatives thereof.
The electron transport region ETR is provided on the emission layer EML. The electron transport region ETR may include at least one of a hole blocking layer HBL, an electron transport layer ETL, or an electron injection layer EIL, but embodiments of the present disclosure are not limited thereto.
The electron transport region ETR may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multilayer structure having a plurality of layers formed using a plurality of different materials.
For example, the electron transport region ETR may have a single layer structure of an electron injection layer EIL or an electron transport layer ETL, or a single layer structure formed using an electron injection material and an electron transport material. In some embodiments, the electron transport region ETR may have a single layer structure having a plurality of different materials, or a structure stacked from the emission layer EML of electron transport layer ETL/electron injection layer EIL, or hole blocking layer HBL/electron transport layer ETL/electron injection layer EIL, without limitation. The thickness of the electron transport region ETR may be, for example, about 100 Å to about 1,500 Å.
The electron transport region ETR may be formed using any suitable method (such as a vacuum deposition method, a spin coating method, a cast method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and/or a laser induced thermal imaging (LITI) method).
When the electron transport region ETR includes an electron transport layer ETL, the electron transport region ETR may include an anthracene-based compound. The electron transport region may include, for example, tris(8-hydroxyquinolinato)aluminum (Alq3), 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene, 2,4,6-tris(3′-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine, bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), 2-(4-(N-phenylbenzimidazolyl-1-ylphenyl)-9,10-dinaphthylanthracene, 1,3,5-tri(1-phenyl-1H-benz[d]imidazol-2-yl)phenyl (TPBi), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (tBu-PBD), bis(2-methyl-8-quinolinolato-N1,O8)-(1,1′-biphenyl-4-olato)aluminum (BAlq), beryllium bis(benzoquinolin-10-olate (Bebq2), 9,10-di(naphthalene-2-yl)anthracene (ADN), or mixtures thereof, without limitation. The thickness of the electron transport layer ETL may be about 100 Å to about 1,000 Å and may be, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer ETL satisfies the above-described range, satisfactory electron transport properties may be obtained without substantial increase of a driving voltage.
When the electron transport region ETR includes the electron injection layer EIL, the electron transport region ETR may include, a metal halide (such as LiF, NaCl, CsF, RbCl, and/or RbI), a lanthanide metal (such as Yb), a metal oxide (such as Li2O and/or BaO), or lithium quinolate (LiQ). However, an embodiment of the present disclosure is not limited thereto. In some embodiments, the electron injection layer EIL may be formed using a mixture material of an electron transport material and an insulating organo metal salt. The organo metal salt may be a material having an energy band gap of about 4 eV or more. The organo metal salt may include, for example, metal acetates, metal benzoates, metal acetoacetates, metal acetylacetonates, and/or metal stearates. The thickness of the electron injection layer EIL may be about 1 Å to about 100 Å, and about 3 Å to about 90 Å. When the thickness of the electron injection layer EIL satisfies the above described range, satisfactory electron injection properties may be obtained without inducing a substantial increase in driving voltage.
The electron transport region ETR may include a hole blocking layer HBL as described above. The hole blocking layer HBL may include, for example, at least one of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), bis[2-(diphenylphosphino)phenyl]ether oxide (DPEPO), or 4,7-diphenyl-1,10-phenanthroline (Bphen). However, embodiments of the present disclosure are not limited thereto.
The second electrode EL2 is provided on the electron transport region ETR. The second electrode EL2 may be a common electrode or a cathode. The second electrode EL2 may be a transmissive electrode, a transflective electrode, or a reflective electrode. When the second electrode EL2 is a transmissive electrode, the second electrode EL2 may include a transparent metal oxide, for example, ITO, IZO, ZnO, ITZO, etc.
When the second electrode EL2 is a transflective electrode or a reflective electrode, the second electrode EL2 may include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF/Ca, LiF/Al, Mo, Ti, compounds thereof, or mixtures thereof (for example, a mixture of Ag and Mg). The second electrode EL2 may have a multilayered structure including a reflective layer or a transflective layer formed using the above-described materials and a transparent conductive layer formed using ITO, IZO, ZnO, ITZO, etc.
In some embodiments, the second electrode EL2 may be connected with an auxiliary electrode. When the second electrode EL2 is connected with the auxiliary electrode, the resistance of the second electrode EL2 may decrease.
Referring to
In an embodiment, the capping layer CPL may be an organic layer or an inorganic layer. For example, when the capping layer CPL includes an inorganic material, the inorganic material may include an alkali metal compound (such as LiF), and/or an alkaline earth compound (such as MgF2, SiON, SiNx, SiOy, etc.)
For example, when the capping layer (CPL) includes an organic material, the organic material may include α-NPD, NPB, TPD, m-MTDATA, Alq3, CuPc, N4,N4,N4′,N4′-tetra(biphenyl-4-yl) biphenyl-4,4′-diamine (TPD15), 4,4′,4″-tris(carbazol-9-yl) triphenylamine (TCTA), etc., or may include an epoxy resin, or acrylate such as methacrylate. However, an embodiment of the present disclosure is not limited thereto, and the capping layer CPL may include an amine compound. For example, the capping layer CPL may include any one among Compounds P1 to P5.
The refractive index of the capping layer CPL may be 1.6 or more. For example, the refractive index of the capping layer CPL may be 1.6 or more with respect to light having a wavelength of about 550 nm to about 660 nm.
In the organic electroluminescence device 10, according to the application of voltages to the first electrode EL1 and the second electrode EL2, respectively, holes injected from the first electrode EL1 move through the hole transport region HTR to the emission layer EML, and electrons injected from the second electrode EL2 move through the electron transport region ETR to the emission layer EML. The electrons and holes may recombine in the emission layer EML to produce excitons, and light may be emitted via transition of the excitons from an excited state to the ground state.
When the organic electroluminescence device 10 is a top emission type, the first electrode EL1 may be a reflective electrode, and the second electrode EL2 may be a transmissive or a transflective electrode. When the organic electroluminescence device 10 is a bottom emission type, the first electrode EL1 may be a transmissive or transflective electrode, and the second electrode EL2 may be a reflective electrode.
The organic electroluminescence device 10 according to an embodiment of the present disclosure includes the polycyclic compound represented by Formula 1, and accordingly, high efficiency and/or long lifespan may be achieved. In addition, a decreased driving voltage may be achieved.
Hereinafter, the present disclosure will be explained referring to embodiments and comparative embodiments. The following example embodiments are only illustrations to assist the understanding of the present disclosure, and the scope of the present disclosure is not limited thereto.
The polycyclic compound according to an embodiment of the present disclosure may be synthesized, for example, as follows. However, the synthetic method of the polycyclic compound according to an embodiment of the present disclosure is not limited thereto.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (140.0 mmol) of 3-chloronaphthalen-1-ol, 29.39 g (1.2 eq, 168.0 mmol) of 1-bromo-2-fluorobenzene, 91.20 g (2.0 eq, 280.0 mmol) of Cs2CO3, and 280 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-1 (32.68 g, yield 70%).
By FAB-MS measurement, mass number m/z=333 was observed as the molecular ion peak, and Intermediate IM-1 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (74.9 mmol) of IM-1, 0.84 g (0.05 eq, 3.7 mmol) of Pd(OAc)2, 15.54 g (1.5 eq, 112.4 mmol) of K2CO3, 1.97 g (0.10 eq, 7.5 mmol) of PPh3, and 300 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-2 (14.20 g, yield 75%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-2 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-2, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.56 g (2.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 7.48 g (1.1 eq, 45.2 mmol) of naphthalene-1-amine, and 0.96 g (0.1 eq, 4.7 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-3 (13.31 g, yield 78%).
By FAB-MS measurement, mass number m/z=359 was observed as the molecular ion peak, and Intermediate IM-3 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (27.8 mmol) of IM-3, 0.48 g (0.03 eq, 0.8 mmol) of Pd(dba)2, 5.35 g (2.0 eq, 55.6 mmol) of NaOtBu, 139 mL of toluene, 6.34 g (1.1 eq, 30.6 mmol) of 1-bromonaphthalene, and 0.56 g (0.1 eq, 2.8 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound A1 (10.94 g, yield 81%) as a solid.
By FAB-MS measurement, mass number m/z=485 was observed as the molecular ion peak, and Compound A1 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (128.4 mmol) of 3-chloronaphthalen-1-thiol, 26.97 g (1.2 eq, 154.1 mmol) of 1-bromo-2-fluorobenzene, 83.68 g (2.0 eq, 256.8 mmol) of Cs2CO3, and 257 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-4 (33.68 g, yield 75%).
By FAB-MS measurement, mass number m/z=349 was observed as the molecular ion peak, and Intermediate IM-4 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (71.5 mmol) of IM-4, 0.80 g (0.05 eq, 3.6 mmol) of Pd(OAc)2, 14.52 g (1.5 eq, 107.2 mmol) of K2CO3, 1.88 g (0.10 eq, 7.1 mmol) of PPh3, and 286 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-5 (13.64 g, yield 71%).
By FAB-MS measurement, mass number m/z=268 was observed as the molecular ion peak, and Intermediate IM-5 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (44.7 mmol) of IM-6, 0.77 g (0.03 eq, 1.3 mmol) of Pd(dba)2, 4.29 g (2.0 eq, 44.7 mmol) of NaOtBu, 224 mL of toluene, 10.77 g (1.1 eq, 49.1 mmol) of 4-(naphthalene-1-yl)aniline, and 0.90 g (0.1 eq, 4.5 mmol) of tBu3P were added in order, followed by heating, refluxing and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-6 (16.74 g, yield 83%).
By FAB-MS measurement, mass number m/z=451 was observed as the molecular ion peak, and Intermediate IM-6 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (22.1 mmol) of IM-6, 0.38 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.26 g (2.0 eq, 44.3 mmol) of NaOtBu, 111 mL of toluene, 5.68 g (1.1 eq, 24.4 mmol) of 4-bromobiphenyl, and 0.45 g (0.1 eq, 2.2 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound A19 (11.10 g, yield 83%) as a solid.
By FAB-MS measurement, mass number m/z=603 was observed as the molecular ion peak, and Compound A19 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (140.0 mmol) of 8-chloronaphthalen-1-ol, 29.39 g (1.2 eq, 168.0 mmol) of 1-bromo-2-fluorobenzene, 91.20 g (2.0 eq, 280.0 mmol) of Cs2CO3, and 280 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-7 (32.22 g, yield 69%).
By FAB-MS measurement, mass number m/z=333 was observed as the molecular ion peak, and Intermediate IM-7 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (74.9 mmol) of IM-7, 0.84 g (0.05 eq, 3.7 mmol) of Pd(OAc)2, 15.54 g (1.5 eq, 112.4 mmol) of K2CO3, 1.97 g (0.10 eq, 7.5 mmol) of PPh3, and 300 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-8 (12.50 g, yield 66%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-8 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (39.6 mmol) of IM-8, 0.68 g (0.03 eq, 1.2 mmol) of Pd(dba)2, 3.80 g (1.0 eq, 39.6 mmol) of NaOtBu, 198 mL of toluene, 7.37 g (1.1 eq, 43.5 mmol) of [1,1′-biphenyl]-3-amine, and 0.80 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-9 (11.75 g, yield 77%).
By FAB-MS measurement, mass number m/z=385 was observed as the molecular ion peak, and Intermediate IM-9 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (25.9 mmol) of IM-9, 0.45 g (0.03 eq, 0.8 mmol) of Pd(dba)2, 4.99 g (2.0 eq, 51.9 mmol) of NaOtBu, 130 mL of toluene, 8.08 g (1.1 eq, 28.5 mmol) of 2-(4-bromophenyl)naphthalene, and 0.52 g (0.1 eq, 2.6 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound A65 (11.59 g, yield 76%) as a solid.
By FAB-MS measurement, mass number m/z=587 was observed as the molecular ion peak, and Compound A65 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (140.0 mmol) of 5-chloronaphthalen-1-ol, 29.39 g (1.2 eq, 168.0 mmol) of 1-bromo-2-fluorobenzene, 91.20 g (2.0 eq, 280.0 mmol) of Cs2CO3, and 280 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-10 (35.02 g, yield 75%).
By FAB-MS measurement, mass number m/z=333 was observed as the molecular ion peak, and Intermediate IM-10 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (74.9 mmol) of IM-10, 0.84 g (0.05 eq, 3.7 mmol) of Pd(OAc)2, 15.54 g (1.5 eq, 112.4 mmol) of K2CO3, 1.97 g (0.10 eq, 7.5 mmol) of PPh3, and 300 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-11 (14.01 g, yield 74%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-11 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-11, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 10.09 g (1.1 eq, 52.2 mmol) of phenanthren-2-amine, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-12 (14.78 g, yield 76%).
By FAB-MS measurement, mass number m/z=409 was observed as the molecular ion peak, and Intermediate IM-12 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (24.4 mmol) of IM-12, 0.42 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.69 g (2.0 eq, 48.8 mmol) of NaOtBu, 122 mL of toluene, 8.95 g (1.1 eq, 26.9 mmol) of 9-(4-bromophenyl)naphthalene, and 0.49 g (0.1 eq, 2.4 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound B49 (12.93 g, yield 80%) as a solid.
By FAB-MS measurement, mass number m/z=661 was observed as the molecular ion peak, and Compound B49 was identified.
Under an Ar atmosphere, to a 2,000 mL, three neck flask, 30.00 g (134.5 mmol) of 2-bromo-1-naphthol, 25.79 g (1.1 eq, 147.9 mmol) of (4-chloro-2-fluorophenyl)boronic acid, 55.76 g (3.0 eq, 403.5 mmol) of K2CO3, 7.77 g (0.05 eq, 6.7 mmol) of Pd(PPh3)4, and 941 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating and stirring at about 80° C. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-13 (28.61 g, yield 78%).
By FAB-MS measurement, mass number m/z=272 was observed as the molecular ion peak, and Intermediate IM-13 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 25.00 g (91.7 mmol) of IM-13, 59.74 g (2.0 eq, 183.4 mmol) of Cs2CO3, and 184 mL of DMSO were added in order, followed by heating to about 110° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-14 (18.30 g, yield 79%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-14 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-14, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 17.42 g (1.1 eq, 52.2 mmol) of 9,9-diphenyl-9H-fluoren-2-amine, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-15 (20.10 g, yield 77%).
By FAB-MS measurement, mass number m/z=549 was observed as the molecular ion peak, and Intermediate IM-15 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (18.2 mmol) of IM-15, 0.31 g (0.03 eq, 0.5 mmol) of Pd(dba)2, 3.50 g (2.0 eq, 36.4 mmol) of NaOtBu, 91 mL of toluene, 6.67 g (1.1 eq, 20.0 mmol) of 9-(4-bromophenyl)phenanthrene, and 0.37 g (0.1 eq, 1.8 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound B94 (11.09 g, yield 76%) as a solid.
By FAB-MS measurement, mass number m/z=801 was observed as the molecular ion peak, and Compound B94 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (140.0 mmol) of 6-chloronaphthalen-1-ol, 29.39 g (1.2 eq, 168.0 mmol) of 1-bromo-2-fluorobenzene, 91.20 g (2.0 eq, 280.0 mmol) of Cs2CO3, and 280 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-16 (36.89 g, yield 79%).
By FAB-MS measurement, mass number m/z=333 was observed as the molecular ion peak, and Intermediate IM-16 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (74.9 mmol) of IM-16, 0.84 g (0.05 eq, 3.7 mmol) of Pd(OAc)2, 15.54 g (1.5 eq, 112.4 mmol) of K2CO3, 1.97 g (0.10 eq, 7.5 mmol) of PPh3, and 300 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-17 (14.20 g, yield 75%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-17 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-17, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 11.45 g (1.1 eq, 52.2 mmol) of 4-(naphthalene-1-yl)aniline, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-18 (15.93 g, yield 77%).
By FAB-MS measurement, mass number m/z=435 was observed as the molecular ion peak, and Intermediate IM-18 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (23.0 mmol) of IM-18, 0.40 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.41 g (2.0 eq, 45.9 mmol) of NaOtBu, 115 mL of toluene, 10.39 g (1.1 eq, 25.3 mmol) of 2-bromo-spiro[fluorene-9,9′-xanthene], and 0.47 g (0.1 eq, 2.3 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound C67 (12.84 g, yield 73%) as a solid.
By FAB-MS measurement, mass number m/z=765 was observed as the molecular ion peak, and Compound C67 was identified.
Under an Ar atmosphere, to a 2,000 mL, three neck flask, 30.00 g (134.5 mmol) of 2-bromo-1-naphthol, 25.79 g (1.1 eq, 147.9 mmol) of (3-chloro-2-fluorophenyl)boronic acid, 55.76 g (3.0 eq, 403.5 mmol) of K2CO3, 7.77 g (0.05 eq, 6.7 mmol) of Pd(PPh3)4, and 941 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating and stirring at about 80° C. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-19 (27.87 g, yield 76%).
By FAB-MS measurement, mass number m/z=272 was observed as the molecular ion peak, and Intermediate IM-19 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 25.00 g (91.7 mmol) of IM-19, 59.74 g (2.0 eq, 183.4 mmol) of Cs2CO3, and 184 mL of DMSO were added in order, followed by heating to about 110° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-20 (17.84 g, yield 77%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-20 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-20, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 8.84 g (1.1 eq, 52.2 mmol) of 4-aminobiphenyl, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-21 (14.64 g, yield 80%).
By FAB-MS measurement, mass number m/z=385 was observed as the molecular ion peak, and Intermediate IM-21 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (25.9 mmol) of IM-21, 0.45 g (0.03 eq, 0.8 mmol) of Pd(dba)2, 4.99 g (2.0 eq, 51.9 mmol) of NaOtBu, 130 mL of toluene, 11.74 g (1.1 eq, 28.5 mmol) of 4′-bromospiro[fluorene-9,9′-xanthene], and 0.52 g (0.1 eq, 2.6 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound C124 (13.93 g, yield 75%) as a solid.
By FAB-MS measurement, mass number m/z=715 was observed as the molecular ion peak, and Compound C124 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-14, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 12.81 g (1.1 eq, 52.2 mmol) of [1,1′:2′,1″-terphenyl]-4-amine, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to an aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-22 (17.53 g, yield 80%).
By FAB-MS measurement, mass number m/z=461 was observed as the molecular ion peak, and Intermediate IM-22 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 15.00 g (32.5 mmol) of IM-22, 0.56 g (0.03 eq, 1.0 mmol) of Pd(dba)2, 6.25 g (1.0 eq, 65.0 mmol) of NaOtBu, 162 mL of toluene, 10.11 g (1.1 eq, 35.7 mmol) of 1-bromo-4-iodobenzene, and 0.66 g (0.1 eq, 3.2 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-23 (16.43 g, yield 82%).
By FAB-MS measurement, mass number m/z=616 was observed as the molecular ion peak, and Intermediate IM-23 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 15.00 g (24.3 mmol) of IM-23, 1.99 g (0.10 eq, 2.4 mmol) of Pd(dppf)Cl2, 4.77 g (2.0 eq, 48.7 mmol) of KOAc, 122 mL of DMF, and 7.41 g (1.2 eq, 29.2 mmol) of bis(pinacolato)diboron were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-24 (12.11 g, yield 75%).
By FAB-MS measurement, mass number m/z=663 was observed as the molecular ion peak, and Intermediate IM-24 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (31.8 mmol) of IM-24, 7.08 g (1.1 eq, 16.6 mmol) of 3-bromo-9,9′-spirobi[xanthene], 6.25 g (3.0 eq, 45.2 mmol) of K2CO3, 0.87 g (0.05 eq, 0.8 mmol) of Pd(PPh3)4, and 105 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating to about 80° C. and stirring. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound C153 (9.72 g, yield 73%) as a solid.
By FAB-MS measurement, mass number m/z=884 was observed as the molecular ion peak, and Compound C153 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (140.0 mmol) of 4-chloronaphthalen-1-ol, 29.39 g (1.2 eq, 168.0 mmol) of 1-bromo-2-fluorobenzene, 91.20 g (2.0 eq, 280.0 mmol) of Cs2CO3, and 280 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-25 (35.49 g, yield 76%).
By FAB-MS measurement, mass number m/z=333 was observed as the molecular ion peak, and Intermediate IM-25 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (74.9 mmol) of IM-25, 0.84 g (0.05 eq, 3.7 mmol) of Pd(OAc)2, 15.54 g (1.5 eq, 112.4 mmol) of K2CO3, 1.97 g (0.10 eq, 7.5 mmol) of PPh3, and 300 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-26 (14.77 g, yield 78%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-26 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-26, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 12.81 g (1.1 eq, 52.2 mmol) of [1,1′:4′,1″-terphenyl]-4-amine, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-27 (17.10 g, yield 78%).
By FAB-MS measurement, mass number m/z=461 was observed as the molecular ion peak, and Intermediate IM-27 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (21.7 mmol) of IM-27, 0.37 g (0.03 eq, 0.6 mmol) of Pd(dba)2, 4.16 g (2.0 eq, 43.3 mmol) of NaOtBu, 108 mL of toluene, 9.90 g (1.1 eq, 23.8 mmol) of 3-bromotetraphenylsilane, and 0.44 g (0.1 eq, 2.2 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound D32 (13.11 g, yield 76%) as a solid.
By FAB-MS measurement, mass number m/z=796 was observed as the molecular ion peak, and Compound D32 was identified.
Under an Ar atmosphere, to a 2,000 mL, three neck flask, 30.00 g (134.5 mmol) of 2-bromo-1-naphthol, 25.79 g (1.1 eq, 147.9 mmol) of (5-chloro-2-fluorophenyl)boronic acid, 55.76 g (3.0 eq, 403.5 mmol) of K2CO3, 7.77 g (0.05 eq, 6.7 mmol) of Pd(PPh3)4, and 941 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating and stirring at about 80° C. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-28 (13.83 g, yield 78%).
By FAB-MS measurement, mass number m/z=272 was observed as the molecular ion peak, and Intermediate IM-28 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 25.00 g (91.7 mmol) of IM-28, 59.74 g (2.0 eq, 183.4 mmol) of Cs2CO3, and 184 mL of DMSO were added in order, followed by heating to about 110° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-29 (18.76 g, yield 81%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-29 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-29, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 7.48 g (1.1 eq, 52.2 mmol) of naphthalene-1-amine, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-30 (12.80 g, yield 75%).
By FAB-MS measurement, mass number m/z=359 was observed as the molecular ion peak, and Intermediate IM-30 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (27.8 mmol) of IM-30, 0.48 g (0.03 eq, 0.8 mmol) of Pd(dba)2, 5.35 g (2.0 eq, 55.6 mmol) of NaOtBu, 139 mL of toluene, 15.04 g (1.1 eq, 30.6 mmol) of [4′-bromo-(1,1′-biphenyl)-4-yl]triphenylsilane, and 0.56 g (0.1 eq, 2.8 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound D162 (15.64 g, yield 73%) as a solid.
By FAB-MS measurement, mass number m/z=770 was observed as the molecular ion peak, and Compound D162 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (140.0 mmol) of 7-chloronaphthalen-1-ol, 29.39 g (1.2 eq, 168.0 mmol) of 1-bromo-2-fluorobenzene, 91.20 g (2.0 eq, 280.0 mmol) of Cs2CO3, and 280 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-31 (35.49 g, yield 76%).
By FAB-MS measurement, mass number m/z=333 was observed as the molecular ion peak, and Intermediate IM-31 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (74.9 mmol) of IM-31, 0.84 g (0.05 eq, 3.7 mmol) of Pd(OAc)2, 15.54 g (1.5 eq, 112.4 mmol) of K2CO3, 1.97 g (0.10 eq, 7.5 mmol) of PPh3, and 300 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-32 (13.63 g, yield 72%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-32 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-32, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 11.45 g (1.1 eq, 52.2 mmol) of 4-(naphthalen-1-yl)aniline, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-33 (16.75 g, yield 81%).
By FAB-MS measurement, mass number m/z=435 was observed as the molecular ion peak, and Intermediate IM-33 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (23.0 mmol) of IM-33, 0.40 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.41 g (2.0 eq, 45.9 mmol) of NaOtBu, 115 mL of toluene, 11.98 g (1.1 eq, 25.3 mmol) of 9-(3-bromotetraphenyl)-3,6-diphenyl-9H-carbazole, and 0.46 g (0.1 eq, 2.3 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound E87 (13.51 g, yield 71%) as a solid.
By FAB-MS measurement, mass number m/z=829 was observed as the molecular ion peak, and Compound E87 was identified.
Under an Ar atmosphere, to a 2,000 mL, three neck flask, 30.00 g (134.5 mmol) of 2-bromo-1-naphthol, 25.79 g (1.1 eq, 147.9 mmol) of (2-chloro-6-fluorophenyl)boronic acid, 55.76 g (3.0 eq, 403.5 mmol) of K2CO3, 7.77 g (0.05 eq, 6.7 mmol) of Pd(PPh3)4, and 941 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating and stirring at about 80° C. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-34 (27.51 g, yield 75%).
By FAB-MS measurement, mass number m/z=272 was observed as the molecular ion peak, and Intermediate IM-34 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 25.00 g (91.7 mmol) of IM-34, 59.74 g (2.0 eq, 183.4 mmol) of Cs2CO3, and 184 mL of DMSO were added in order, followed by heating to about 110° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-35 (18.30 g, yield 79%).
By FAB-MS measurement, mass number m/z=252 was observed as the molecular ion peak, and Intermediate IM-35 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-35, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 10.09 g (1.1 eq, 52.2 mmol) of 9-aminophenanthrene, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-36 (14.58 g, yield 75%).
By FAB-MS measurement, mass number m/z=650 was observed as the molecular ion peak, and Intermediate IM-36 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (24.4 mmol) of IM-36, 0.42 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.69 g (2.0 eq, 48.8 mmol) of NaOtBu, 122 mL of toluene, 8.66 g (1.1 eq, 26.9 mmol) of 9-(4-bromophenyl)-9H-carbazole, and 0.49 g (0.1 eq, 2.4 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound E190 (11.12 g, yield 70%) as a solid.
By FAB-MS measurement, mass number m/z=650 was observed as the molecular ion peak, and Compound E190 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-2, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 17.42 g (1.1 eq, 52.2 mmol) of 9,9-diphenyl-9H-fluoren-4-amine, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-37 (19.05 g, yield 73%).
By FAB-MS measurement, mass number m/z=549 was observed as the molecular ion peak, and Intermediate IM-37 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (18.2 mmol) of IM-37, 0.31 g (0.03 eq, 0.5 mmol) of Pd(dba)2, 3.50 g (2.0 eq, 36.4 mmol) of NaOtBu, 91 mL of toluene, 7.97 g (1.1 eq, 20.0 mmol) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole, and 0.37 g (0.1 eq, 1.8 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound F15 (11.83 g, yield 75%) as a solid.
By FAB-MS measurement, mass number m/z=867 was observed as the molecular ion peak, and Compound F15 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (47.5 mmol) of IM-14, 0.82 g (0.03 eq, 1.4 mmol) of Pd(dba)2, 4.57 g (1.0 eq, 47.5 mmol) of NaOtBu, 237 mL of toluene, 8.84 g (1.1 eq, 52.2 mmol) of [1,1′-biphenyl]-2-amine, and 0.96 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to an aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-38 (14.46 g, yield 79%).
By FAB-MS measurement, mass number m/z=385 was observed as the molecular ion peak, and Intermediate IM-38 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 14.00 g (36.3 mmol) of IM-38, 0.63 g (0.03 eq, 1.1 mmol) of Pd(dba)2, 6.98 g (1.0 eq, 72.6 mmol) of NaOtBu, 182 mL of toluene, 11.30 g (1.1 eq, 40.0 mmol) of 1-bromo-4-iodobenzene, and 0.73 g (0.1 eq, 3.6 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-39 (14.33 g, yield 73%).
By FAB-MS measurement, mass number m/z=540 was observed as the molecular ion peak, and Intermediate IM-39 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 13.00 g (24.1 mmol) of IM-39, 1.96 g (0.10 eq, 2.4 mmol) of Pd(dppf)Cl2, 4.72 g (2.0 eq, 48.1 mmol) of KOAc, 120 mL of DMF, and 7.33 g (1.2 eq, 28.9 mmol) of bis(pinacolato)diboron were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-40 (10.74 g, yield 76%).
By FAB-MS measurement, mass number m/z=587 was observed as the molecular ion peak, and Intermediate IM-40 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (17.0 mmol) of IM-40, 7.46 g (1.1 eq, 18.7 mmol) of 3-(3-bromophenyl)-9-phenyl-9H-carbazole, 7.05 g (3.0 eq, 51.1 mmol) of K2CO3, 0.98 g (0.05 eq, 0.9 mmol) of Pd(PPh3)4, and 119 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating to about 80° C. and stirring. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound F146 (10.47 g, yield 79%) as a solid.
By FAB-MS measurement, mass number m/z=778 was observed as the molecular ion peak, and Compound F146 was identified.
Under an Ar atmosphere, to a 2,000 mL, three neck flask, 30.00 g (134.5 mmol) of 2-bromo-1-naphthol, 37.47 g (1.1 eq, 147.9 mmol) of (3-bromo-6-chloro-2-fluorophenyl)boronic acid, 55.76 g (3.0 eq, 403.5 mmol) of K2CO3, 7.77 g (0.05 eq, 6.7 mmol) of Pd(PPh3)4, and 941 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating and stirring at about 80° C. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-41 (35.00 g, yield 74%).
By FAB-MS measurement, mass number m/z=351 was observed as the molecular ion peak, and Intermediate IM-41 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 30.00 g (85.3 mmol) of IM-41, 55.60 g (2.0 eq, 170.6 mmol) of Cs2CO3, and 170 mL of DMSO were added in order, followed by heating to about 110° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-42 (22.63 g, yield 80%).
By FAB-MS measurement, mass number m/z=331 was observed as the molecular ion peak, and Intermediate IM-42 was identified.
Under an Ar atmosphere, to a 1,000 mL, three neck flask, 20.00 g (60.3 mmol) of IM-42, 8.09 g (1.1 eq, 66.3 mmol) of phenylboronic acid, 25.01 g (3.0 eq, 180.9 mmol) of K2CO3, 3.48 g (0.05 eq, 3.0 mmol) of Pd(PPh3)4, and 422 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, followed by heating and stirring at about 80° C. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-43 (16.26 g, yield 82%).
By FAB-MS measurement, mass number m/z=328 was observed as the molecular ion peak, and Intermediate IM-43 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (36.5 mmol) of IM-43, 0.63 g (0.03 eq, 1.1 mmol) of Pd(dba)2, 3.51 g (1.0 eq, 36.5 mmol) of NaOtBu, 182 mL of toluene, 10.81 g (1.1 eq, 40.1 mmol) of 4-(phenanthren-9-yl)aniline, and 0.74 g (0.1 eq, 3.6 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-44 (15.78 g, yield 77%).
By FAB-MS measurement, mass number m/z=561 was observed as the molecular ion peak, and Intermediate IM-44 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (17.8 mmol) of IM-44, 0.31 g (0.03 eq, 0.5 mmol) of Pd(dba)2, 3.42 g (2.0 eq, 35.6 mmol) of NaOtBu, 89 mL of toluene, 7.80 g (1.1 eq, 19.6 mmol) of 3-(4-bromophenyl)-9-phenyl-9H-carbazole, and 0.36 g (0.1 eq, 1.8 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound F198 (11.89 g, yield 76%) as a solid.
By FAB-MS measurement, mass number m/z=879 was observed as the molecular ion peak, and Compound F198 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (156.0 mmol) of naphthalene-1-thiol, 39.21 g (1.2 eq, 187.2 mmol) of 1-bromo-3-chloro-2-fluorobenzene, 101.67 g (2.0 eq, 312.1 mmol) of Cs2CO3, and 312 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-45 (38.74 g, yield 71%).
By FAB-MS measurement, mass number m/z=349 was observed as the molecular ion peak, and Intermediate IM-45 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (71.5 mmol) of IM-45, 0.80 g (0.05 eq, 3.6 mmol) of Pd(OAc)2, 14.52 g (1.5 eq, 107.2 mmol) of K2CO3, 1.88 g (0.10 eq, 7.1 mmol) of PPh3, and 286 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-46 (14.99 g, yield 71%).
By FAB-MS measurement, mass number m/z=268 was observed as the molecular ion peak, and Intermediate IM-46 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (44.7 mmol) of IM-46, 0.77 g (0.03 eq, 1.3 mmol) of Pd(dba)2, 4.29 g (2.0 eq, 44.7 mmol) of NaOtBu, 224 mL of toluene, 10.77 g (1.1 eq, 49.1 mmol) of 4-(naphthalen-1-yl)aniline, and 0.90 g (0.1 eq, 4.5 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-47 (16.13 g, yield 80%).
By FAB-MS measurement, mass number m/z=451 was observed as the molecular ion peak, and Intermediate IM-47 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (22.1 mmol) of IM-47, 0.38 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.26 g (2.0 eq, 44.3 mmol) of NaOtBu, 111 mL of toluene, 6.90 g (1.1 eq, 24.4 mmol) of 1-(4-bromophenyl)naphthalene, and 0.45 g (0.1 eq, 2.2 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound A127 (12.31 g, yield 85%) as a solid.
By FAB-MS measurement, mass number m/z=653 was observed as the molecular ion peak, and Compound A127 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (156.0 mmol) of naphthalen-1-thiol, 39.21 g (1.2 eq, 187.2 mmol) of 1-bromo-3-chloro-fluorobenzene, 101.67 g (2.0 eq, 312.1 mmol) of Cs2CO3, and 312 mL of DMSO were added in order, followed by heating and stirring at about 110° C. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-48 (41.46 g, yield 76%).
By FAB-MS measurement, mass number m/z=349 was observed as the molecular ion peak, and Intermediate IM-48 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 25.00 g (71.5 mmol) of IM-48, 0.80 g (0.05 eq, 3.6 mmol) of Pd(OAc)2, 14.52 g (1.5 eq, 107.2 mmol) of K2CO3, 1.88 g (0.10 eq, 7.1 mmol) of PPh3, and 286 mL of DMA were added in order, followed by heating to about 140° C. and stirring. After cooling to room temperature, water was added to the reaction solution, and the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-49 (12.68 g, yield 77%).
By FAB-MS measurement, mass number m/z=268 was observed as the molecular ion peak, and Intermediate IM-49 was identified.
Under an Ar atmosphere, to a 500 mL, three neck flask, 12.00 g (44.7 mmol) of IM-49, 0.77 g (0.03 eq, 1.3 mmol) of Pd(dba)2, 4.29 g (2.0 eq, 44.7 mmol) of NaOtBu, 224 mL of toluene, 10.77 g (1.1 eq, 49.1 mmol) of 4-(naphthalen-1-yl)aniline, and 0.90 g (0.1 eq, 4.5 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Intermediate IM-50 (16.08 g, yield 78%).
By FAB-MS measurement, mass number m/z=451 was observed as the molecular ion peak, and Intermediate IM-50 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (22.1 mmol) of IM-50, 0.38 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.26 g (2.0 eq, 44.3 mmol) of NaOtBu, 111 mL of toluene, 6.88 g (1.1 eq, 24.4 mmol) of 2-(4-chlorophenyl)phenanthrene, and 0.45 g (0.1 eq, 2.2 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound B138 (12.20 g, yield 80%) as a solid.
By FAB-MS measurement, mass number m/z=703 was observed as the molecular ion peak, and Compound B138 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (23.0 mmol) of IM-18, 0.40 g (0.03 eq, 0.7 mmol) of Pd(dba)2, 4.41 g (2.0 eq, 45.9 mmol) of NaOtBu, 115 mL of toluene, 5.23 g (1.1 eq, 25.3 mmol) of 1-bromonaphthalene, and 0.46 g (0.1 eq, 2.3 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound A173 (9.03 g, yield 70%) as a solid.
By FAB-MS measurement, mass number m/z=561 was observed as the molecular ion peak, and Compound A173 was identified. 19. Synthesis of Compound A195
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (39.6 mmol) of IM-20, 0.68 g (0.03 eq, 1.2 mmol) of Pd(dba)2, 7.61 g (2.0 eq, 79.1 mmol) of NaOtBu, 198 mL of toluene, 18.35 g (1.1 eq, 43.5 mmol) of bis[4-(naphthalen-2-yl)phenyl]amine, and 0.80 g (0.1 eq, 4.0 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound A195 (19.43 g, yield 77%) as a solid.
By FAB-MS measurement, mass number m/z=637 was observed as the molecular ion peak, and Compound A195 was identified.
Under an Ar atmosphere, to a 300 mL, three neck flask, 10.00 g (27.8 mmol) of IM-30, 0.48 g (0.03 eq, 0.8 mmol) of Pd(dba)2, 5.35 g (2.0 eq, 55.6 mmol) of NaOtBu, 139 mL of toluene, 10.20 g (1.1 eq, 30.6 mmol) of 9-(4-bromophenyl)phenanthrene, and 0.56 g (0.1 eq, 2.8 mmol) of tBu3P were added in order, followed by heating, refluxing, and stirring. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separated. Toluene was added to the aqueous layer, and further organic layers were extracted. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was separated by filtering, an organic layer was concentrated, and the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as an eluent) to obtain Compound B189 (12.93 g, yield 76%) as a solid.
By FAB-MS measurement, mass number m/z=611 was observed as the molecular ion peak, and Compound B189 was identified.
Organic electroluminescence devices were manufactured using Example Compounds and Comparative Compounds as materials for a hole transport region:
Each of the organic electroluminescence devices of the Examples and Comparative Examples was manufactured using the method below. ITO with a thickness of about 150 nm was patterned on a glass substrate, washed with ultra-pure water, and treated with UV-ozone for about 10 minutes to form a first electrode. Then, 1-TNATA was deposited to a thickness of about 60 nm, and a hole transport layer with a thickness of about 30 nm was formed using each of the Example Compounds or the Comparative Compounds. Then, an emission layer with a thickness of about 25 nm was formed using ADN doped with 3% TBP, and on the emission layer, a layer with a thickness of about 25 nm was formed using Alq3, and a layer with a thickness of about 1 nm was formed using LiF to form an electron transport region. After that, a second electrode with a thickness of about 100 nm was formed using aluminum (Al). Then, Compound P4 was deposited to a thickness of about 70 nm to form a capping layer. Each layer was formed by a vacuum deposition method.
The emission efficiencies of the organic electroluminescence devices according to Examples to 20 and Comparative Examples 1 to 18 are shown in Table 1. The efficiency was measured at a current density of about 10 mA/cm2, and the half life LT50 is the time elapsed for the luminance to fall from an initial value of about 1,000 cd/m2 to half.
Referring to Table 1, it could be confirmed that each of Examples 1 to 20 exhibited a lower voltage, a longer life and a higher efficiency than each of Comparative Examples 1 to 18.
The polycyclic compound according to the present disclosure has a core structure including benzonaphthofuran or benzonaphthothiophene combined with an amine group having a particular substituent, and without being bound by the correctness of any theory or explanation, this structure supports a decreased driving voltage, and increased lifespan and efficiency in an organic electroluminescence device. It is thought that the heteroatom (e.g., O or S) included in the core structure of benzonaphthofuran or benzonaphthothiophene improves hole transport capacity, such that the recombination probability of holes and electrons in an emission layer is improved, and the emission efficiency is improved.
Examples 1 to 4, 6, 9, 11, 13 and 18 each include a compound in which the amine group is bound to the naphthalene ring in the core structure of benzonaphthofuran or benzonaphthothiophene, and exhibit improved device life. Without being bound by the correctness of any theory or explanation, it is believed that because rr electrons around the amine were widely expanded in the naphthalene ring, stability of radical states was enhanced.
Examples 5, 7, 8, 10, 12, 14 to 17, 19 and 20 each include a compound in which the amine group is bound to the benzene ring in the core structure of benzonaphthofuran or benzonaphthothiophene, and exhibit improved emission efficiency. Without being bound by the correctness of any theory or explanation, it is believed that because the heteroatom included in the benzonaphthofuran or benzonaphthothiophene skeleton and the nitrogen atom of an amine group are substituted on the same ring, hole transport effects due to the heteroatom were enhanced.
Comparative Examples 1 and 2 each showed reduced emission efficiency and lifespan when compared with the Examples. Comparative Examples 1 and 2 are compounds in which an amine group is combined with the core structure of benzonaphthofuran or benzonaphthothiophene, but an unsubstituted phenyl group is combined with a nitrogen atom (e.g., the amine group includes only unsubstituted phenyl groups). Without being bound by the correctness of any theory or explanation, it is believed that the glass transition temperature (Tg) of the material was insufficient such that the charge tolerance of the unsubstituted phenyl group was low, and the materials were deteriorated during continuous driving.
Comparative Example 3 showed reduced device efficiency and life when compared with the Examples. Comparative Example 3 is a compound in which benzonaphthofuran and an amine group are combined via a linker (e.g., an intervening phenyl ring), such that the planarity of a molecule was increased, and decomposition occurred during deposition for forming a hole transport layer.
Comparative Example 4 showed reduced device efficiency and life when compared with the Examples. In the compound of Comparative Example 4, a phenyl substituent on the amine is substituted with a fluorenyl group, and without being bound by the correctness of any theory or explanation, it is believed that instability of the sp3 carbon in the fluorenyl group resulted in decomposition under a radical state and high temperature conditions.
In contrast, the polycyclic compounds of Examples 6 to 8 including a spirocyclic structure with a heteroatom showed improved stability, and provided excellent device properties. In Example 5, because a nitrogen atom was combined on (e.g., directly bonded to) a fluorene ring, the stability of a material was improved due to multi-resonance effects. Accordingly, improved emission efficiency and life were exhibited compared with Comparative Example 4.
Comparative Examples 5 and 6 showed particularly reduced emission efficiencies when compared with Examples 6 to 8. Without being bound by the correctness of any theory or explanation, it is believed that because a heteroatom was not included in the spirocycle of the compounds of Comparative Examples 5 and 6, hole transport properties were degraded, and the recombination probability of holes and electrons in an emission layer was decreased.
Comparative Examples 7 and 8 are amine compounds including a triphenylene substituent, and without being bound by the correctness of any theory or explanation, it is believed that because the planarity of the molecule was increased, the molecule was decomposed during hole transport layer formation, and device efficiency and lifespan were both (e.g., simultaneously) degraded.
Comparative Example 9 is an amine compound including a (2,4,6-triphenyl)phenyl group. Without being bound by the correctness of any theory or explanation, it is thought that because the volume around the nitrogen atom is excessively large, the molecule was decomposed during hole transport layer formation, and device efficiency and lifespan were both degraded.
In addition, though an amine group having a phenanthrene group may be combined with the core structure of benzonaphthofuran similar to the present disclosure, the effect on device efficiency and lifespan may depend on the type (e.g., position) of substituent. For example, if the amine group is at position 2 of Chemical Formula 1 or at position 3 of Chemical Formula 1 as in Comparative Example 10, device efficiency and lifespan are both degraded. Without being bound by the correctness of any theory or explanation, it is thought that in this case, the planarity of the molecule as a whole was increased, intermolecular stacking was enhanced, and hole transport properties were deteriorated.
In contrast, as confirmed in Examples 6 and 11, when Ar1 and Ar2 are substituents including a heteroatom, hole transport properties are improved due to the influence of the heteroatom in Ar1 and Ar2, and excellent device properties may be shown observed regardless of the position at which the amine group is bound to the core structure. In addition, as shown in Example 18, when Ar1 and Ar2 are substituents having polycyclic aromatic rings, interactions between the polycyclic aromatic rings of Ar1 and Ar2 and the emission layer host material may be enhanced, hole transport properties may be improved, and excellent device properties may be shown.
Comparative Examples 11 and 12 have a structure in which an amine group having a naphthyl substituent is combined with a benzonaphthofuran core structure, similar to the polycyclic compound of the present disclosure. However, compared with the polycyclic compound of the present disclosure, the position of the amine group is different. In the compounds of Comparative Examples 11 and 12, the oxygen atom and the nitrogen atom are ortho- or para- to each other on the benzene ring, which induces electronic instability, and device efficiency and lifespan were both degraded when compared with the Examples.
By comparison to Example 9, however, when the oxygen atom and the nitrogen atom in the benzonaphthofuran ring are para to each other on the naphthalene ring, electrons may be expanded (e.g., due to resonance) so that the molecular structure may be stabilized, and excellent device properties may be shown.
Further, as confirmed in Examples 7 and 10, when the amine has a substituent having a heteroatom, the electronic instability issue may be solved due to the effects of the heteroatom, and excellent device properties may be shown regardless of the combination position of the amine group. For example, it could be confirmed that if an amine group does not have a substituent including a heteroatom, the bonding position of the nitrogen atom with benzonaphthofuran or benzonaphthothiophene significantly influences device properties, and only a case where the amine group is combined at a specific position showed improved efficiency and life.
In addition, as confirmed in Examples 16 and 17, in a compound having a benzonaphthothiophene core, even when a sulfur atom and a nitrogen atom are combined at ortho or para position, excellent device properties are shown. Compared with an oxygen atom, a sulfur atom has smaller electronegativity (e.g., is less electronegative), and electrons may be more delocalized around the ring. Accordingly, even when the nitrogen atom is bound ortho or para to the sulfur atom, the electronic instability issue may be solved, and efficiency and lifespan may be improved.
Comparative Examples 13 and 15 each include a dibenzoheterole substituent on the amine, but carrier balance is collapsed, and device efficiency and lifespan were both degraded compared with the Examples. Comparative Example 14 includes a benzoxanthene substituent on the amine, but the heat resistance of the benzoxanthene skeleton is insufficient, and device efficiency and lifespan were both degraded when compared with the Examples.
Comparative Examples 16 and 17 are amine compounds having a carbazole group substituents, but the binding positions of the carbazole groups are different from the materials of the Examples, and the device efficiency and lifespan were both degraded when compared with the Examples. In contrast, in the polycyclic compound according to the present disclosure, the amine moiety is bound to position 3 or position 9 of the carbazole ring, which are the most electron-rich positions, such that hole transport properties were improved, and emission efficiency was improved.
Comparative Example 18 is an amine compound having a dibenzofuran substituent, and thermal and charge tolerance were degraded, and device efficiency and lifespan were both degraded compared with the Examples.
The polycyclic compound according to an embodiment of the present disclosure may be included in a hole transport region to contribute to the decrease of the driving voltage and the increase of the efficiency and lifespan of an organic electroluminescence device.
The organic electroluminescence device according to an embodiment of the present disclosure may have excellent efficiency.
The polycyclic compound according to an embodiment of the present disclosure may be used as a material for the hole transport region of an organic electroluminescence device, and the efficiency of the organic electroluminescence device may be improved by the compound.
As used herein, the terms “substantially,” “about,” and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art.
Any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
Although example embodiments of the present disclosure have been described, it is understood that the present disclosure is not limited to these example embodiments, and that various changes and modifications can be made by one of ordinary skill in the art that would be within the spirit and scope of the present disclosure, as set forth in the following claims and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0056177 | May 2020 | KR | national |
