CN110249030B

CN110249030B - Organic electroluminescent device

Info

Publication number: CN110249030B
Application number: CN201880006080.8A
Authority: CN
Inventors: 李舜昌; 郑在皓; 姜炫彬; 俞智雄; 洪尚薫
Original assignee: Material Science Co Ltd
Current assignee: Material Science Co Ltd
Priority date: 2017-01-05
Filing date: 2018-01-05
Publication date: 2023-04-18
Anticipated expiration: 2038-01-05
Also published as: CN110249030A; KR20180081005A; KR102095449B1

Abstract

The present invention relates to an organic electroluminescent device, and more particularly, to an organic electroluminescent device including a novel pyrene-based organic compound and anthracene-based organic compound in at least one organic layer included in the organic electroluminescent device.

Description

Organic electroluminescent device

Technical Field

The present invention relates to an organic electroluminescent device, and more particularly, to an organic electroluminescent device including a novel pyrene-based organic compound and an anthracene-based organic compound in at least one organic layer included in the organic electroluminescent device.

Background

Since the initial organic electroluminescent (OLED) device (C.W.Tang, S.A.Vanslyke, applied Physics Letters, volume 51, page 913, 1987) was developed by c.w. tang of Kodak corporation in the united states using aluminum compounds as the light-emitting layer in aromatic diamines (diamines), research into organic electroluminescent devices of a multilayer thin film structure type and organic materials in organic electroluminescent devices (OLEDs) has been actively conducted. Organic electroluminescent devices have advantages of simple structure and various manufacturing processes, and have high brightness and excellent viewing angle characteristics, compared with other flat panel display devices such as a conventional Liquid Crystal Display (LCD), a Plasma Display Panel (PDP), and a Field Emission Display (FED), and are being commercialized as a backlight, illumination, and advertisement board of a flat panel display such as a wall-mounted Television (TV) or the like, since a response speed is high and a driving voltage is low.

In general, an organic electroluminescent device is a device in which a Hole (Hole) in a light emitting layer meets electrons and emits light when a voltage is applied to a cathode (electron injection electrode) and an anode (Hole injection electrode), and has a structure including a plurality of organic layers between the two electrodes. At this time, the organic electroluminescent device may include a hole injection layer (HIL, hole Injection Layer), a hole transport layer (HTL, hole Transport Layer), an electron transport layer (ETL, electron Transport Layer), or an electron injection layer (EIL, electron Injection Layer) in addition to the light emitting layer (EML, light Emitting Layer), and may further include an electron blocking layer (EBL, electron Blocking Layer) or a hole blocking layer (HBL, hole Blocking Layer) as needed in order to improve the efficiency of the light emitting layer. The organic electroluminescent device in which each of these organic layers is comprised has a structure in which anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode are laminated in this order.

On the other hand, when only one substance is used as the light-emitting substance used in the light-emitting layer, there is a problem in that the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity is lowered or the efficiency of the device is lowered due to the light-emission attenuation effect. Therefore, host/dopant species may be used as a light emitting material to increase light emitting efficiency through an increase in color purity and energy transfer.

The principle is that when a dopant having a smaller energy band gap than a host forming the light emitting layer is mixed in a small amount to the light emitting layer, excitons generated in the light emitting layer are transported as dopants to emit light with high efficiency. At this time, the wavelength of the host shifts to the wavelength band of the dopant, and thus light of a desired wavelength can be obtained according to the kind of dopant used.

The light emitting layer is composed of a red host/dopant, a green host/dopant, and a blue host/dopant, respectively, and the blue light emitting layer is at the greatest disadvantage in terms of lifetime, efficiency, and color purity as compared with other respective colors, so research and development of hosts and dopants capable of realizing excellent blue color are required.

Recently, it has become important that the blue host in the existing polyaromatic system (Polyaromatic System) be substituted for polar derivatives such as Dibenzofuran (Dibenzofuran). The reason for this is that the polarization (polar mobility) and the Dipole Moment (Dipole Moment) increase due to oxygen molecules contained in Dibenzofuran (Dibenzofuran). This characteristic increases the accumulation (Packing) of host molecules in the device, and thus has an effect of improving the driving voltage and efficiency of the device and increasing the lifetime of the device. However, in spite of such characteristics, in the case where the polarity of the host is increased, there is a phenomenon in which the maximum emission wavelength of conventionally used blue dopants is shifted mostly to a long wavelength (red), and thus it is found to be particularly important to find an ideal host/dopant combination.

Disclosure of Invention

An object of the present invention is to provide a host/dopant system that minimizes a phenomenon of shift of a maximum emission wavelength to a long wavelength (red color) when a compound contained in Dibenzofuran (Dibenzofuran) is used as a host, and finally, to provide an organic electroluminescent device having excellent color purity and having characteristics of low driving voltage, high emission efficiency, long lifetime, and the like.

The terminology used in the description presented herein is for the purpose of describing particular embodiments and is not intended to be limiting of the invention. As used in this specification, the singular forms may include the plural unless the context clearly indicates otherwise. Moreover, the use of "comprises" and/or "comprising" in this specification is intended to specify the presence of stated features, values, steps, operations, components, elements, and/or combinations thereof, but does not preclude the presence or addition of at least one other feature, value, operation, component, element, and/or combination thereof.

As used in this specification, the term "and/or" includes all combinations of one and at least one of the corresponding listed items.

In the present invention, "alkyl" means a monovalent substituent derived from a saturated hydrocarbon having 1 to 40 carbon atoms, which is straight or branched. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl, and the like.

In the present invention, "alkenyl" refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), and 2-butenyl (2-butenyl), but are not limited thereto.

In the present invention, "alkynyl" means a monovalent substituent derived from a linear or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl (ethyl), 2-propynyl (2-propynyl) and the like.

In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms which is formed by a single ring or a combination of two or more rings. Further, two or more rings may be attached (suspended) or condensed to each other. Examples of such aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, anthracyl, and dimethylfluorenyl.

In the present invention, "heteroaryl" means a monovalent substituent derived from a mono-or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, at least one carbon in the ring is substituted with a heteroatom such as N, O, S or Se, and preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S or Se. Further, two or more rings may be attached to each other or condensed, or condensed with an aryl group. Examples of such heteroaryl groups include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and triazinyl, polycyclic rings such as phenolthienyl (phenolthienyl), indolizinyl (indolizinyl), indolyl (indoyl), purinyl (purinyl), quinolinyl (quinolyl), benzothiazole (benzothiazole), carbazolyl (carbazolyl) and the like, and 2-purinyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl and 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, an "aryloxy group" is a monovalent substituent represented by RO-, and R refers to an aryl group having 6 to 60 carbon atoms. Examples of such an aryloxy group include, but are not limited to, phenoxy, naphthoxy, and diphenyloxy.

In the present invention, an "alkoxy group" is a monovalent substituent represented by R' O-which refers to an alkyl group having 1 to 40 carbon atoms, and may include a straight chain (linear), branched, or cyclic (cyclic) structure. Examples of the alkoxy group include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, and pentoxy.

In the present invention, "aromatic amine" means an amine substituted with an aryl group having 6 to 60 carbon atoms.

In the present invention, "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl (norbornyl), and adamantane (amantine).

In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, at least one carbon in the ring being substituted with a heteroatom such as N, O, S or Se, and preferably 1 to 3 carbons in the ring being substituted with a heteroatom such as N, O, S or Se. Examples of such a heterocycloalkyl group include, but are not limited to, morpholino and piperazino.

In the present invention, "alkylsilyl" refers to a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and "arylsilyl" refers to a silyl group substituted with an aryl group having 6 to 60 carbon atoms.

In the present invention, "fused ring" refers to a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combination thereof.

In order to achieve the object, there is provided an organic electroluminescent device including a first electrode, a second electrode, and at least one organic film between the first electrode and the second electrode, the organic film of the organic electroluminescent device including at least one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, the light emitting layer including a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.

Chemical formula 1

In the method, in the process of the invention,

L₁by containing C₁、C₂C (C)₃To form C₄～C₇A saturated or unsaturated condensed ring of (C)₁～C₁₀An alkyl group is substituted and a substituent is substituted,

R₁to R₈Are the same or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, halogen, nitro, cyano, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaralkyl having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms and substituted or unsubstituted aryloxy having 6 to 30 carbon atoms,

Chemical formula 2

In the method, in the process of the invention,

R₁₁to R₂₀Are identical or different from each other and at least one is-L₂-Ar₁and/or-L₃-Ar₂,

L₂L and L₃Are identical or different from each other and are each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms,

Ar₁ar and Ar₂Are the same or different from each other and are each independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,

In addition to-L₂-Ar₁or-L₃-Ar₂R outside₁₁To R₂₀Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 24 carbon atomsAlkynyl, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms, and substituted or unsubstituted heteroaralkyl having 3 to 30 carbon atoms,

the R is₁To R₈、L₂To L₃、Ar₁To Ar₂R is R₁₁To R₂₀And may also be composed of groups each independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, substituted or unsubstituted alkyl of 1 to 30 carbon atoms, substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl of 2 to 24 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, substituted or unsubstituted heteroalkyl of 2 to 30 carbon atoms, substituted or unsubstituted aralkyl of 7 to 30 carbon atoms, substituted or unsubstituted aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 2 to 30 carbon atoms, substituted or unsubstituted heteroaralkyl of 3 to 30 carbon atoms, substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, substituted or unsubstituted alkylamino of 1 to 30 carbon atoms, substituted or unsubstituted arylamino of 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino of 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino of 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl of 1 to 30 carbon atoms, and at least one of the same groups when they are present, or at least one of the substituted or unsubstituted silyl groups of carbon atoms and unsubstituted aryl groups of 6 to 30 carbon atoms.

In an example of the present invention, the compound represented by the chemical formula 1 represents a compound represented by the following chemical formula 3.

Chemical formula 3

In the method, in the process of the invention,

R₉r is R₁₀Are the same or different from each other and are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, halogen, cyano group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms and an arylsilyl group having 6 to 30 carbon atoms,

the R is₉R is R₁₀But may also be substituted with at least one substituent independently selected from the group consisting of hydrogen, deuterium, urethane groups, carboxyl groups, cyano groups, nitro groups, halogen groups, hydroxyl groups, carboxylic acid ester groups, alkyl groups of 1 to 30 carbon atoms, alkenyl groups of 2 to 30 carbon atoms, alkynyl groups of 2 to 24 carbon atoms, cycloalkyl groups of 3 to 30 carbon atoms, and heteroalkyl groups of 2 to 30 carbon atoms, and when a plurality of the substituents are present, they are the same or different from each other,

n is an integer of 1 to 3,

R₁to R₈As defined in the invention claim 1.

In one embodiment of the present invention, R of formula 1₁To R₈Any one represents a functional group represented by the following chemical formula 4.

Chemical formula 4

Chemical formula 5

In the method, in the process of the invention,

l is a single bond, substituted or unsubstituted C₆-C₁₈Arylene or substituted or unsubstituted C₆-C₁₈A heteroarylene group, a heteroaryl group,

m is hydrogen, tritium or a functional group represented by the chemical formula 5,

Ar₃ar and Ar₄Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl of 2 to 24 carbon atoms, substituted or unsubstituted heteroalkyl of 2 to 30 carbon atoms, substituted or unsubstituted aralkyl of 7 to 30 carbon atoms, substituted or unsubstituted aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 2 to 30 carbon atoms, and substituted or unsubstituted C₆-C₃₀Heteroaralkyl, substituted or unsubstituted alkylsilyl of 1 to 30 carbon atoms and arylsilyl of 6 to 30 carbon atoms, or said Ar₃Ar and Ar₄Can be linked to form a 6-to 18-membered ring comprising at least one N, O or S,

said L, ar₃Ar and Ar₄And may be substituted with at least one substituent independently selected from the group consisting of hydrogen, deuterium, carbamate, carboxyl, cyano, nitro, halogen, hydroxyl, carboxylate, alkyl of 1 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkynyl of 2 to 24 carbon atoms, cycloalkyl of 3 to 30 carbon atoms, heteroalkyl of 2 to 30 carbon atoms, aralkyl of 7 to 30 carbon atoms, aryl of 6 to 30 carbon atoms, heteroaryl of 2 to 30 carbon atoms, heteroaralkyl of 3 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, alkylamino of 1 to 30 carbon atoms, arylamino of 6 to 30 carbon atoms, aralkylamino of 6 to 30 carbon atoms, heteroarylamino of 2 to 24 carbon atoms, alkylsilyl of 1 to 30 carbon atoms, arylsilyl of 6 to 30 carbon atoms and aryloxy of 6 to 30 carbon atoms, when a plurality of the substituents are present, they are the same or different from each other.

In one embodiment of the present invention, ar of formula 5₃Ar and Ar₄Represents a substituent selected from the group consisting of compounds represented by the following chemical formulas 6 to 11.

Chemical formula 6

Chemical formula 7

Chemical formula 8

Chemical formula 9

Chemical formula 10

Chemical formula 11

In the method, in the process of the invention,

* In order to form part of the bond,

p is an integer of 0 to 4,

q is an integer of 0 to 3,

X₁selected from C (R)₂₃) In the group consisting of N, S and O,

X₂、X₃、X₄x is X₆Are identical or different from each other and are each independently selected from C (R₂₃)(R₂₄)、N(R₂₃) In the group consisting of S and O,

X₅x is X₇Are identical or different from each other and are each independently C (R₂₃) Or N, or a combination of two,

R₂₁to R₂₄Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl of 2 to 24 carbon atoms, substituted or unsubstituted heteroalkyl of 2 to 30 carbon atoms, substituted or unsubstituted aralkyl of 7 to 30 carbon atoms, substituted or unsubstituted aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 2 to 30 carbon atoms, and substituted or unsubstituted C₆-C₃₀Heteroaralkyl, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and an arylsilyl group having 6 to 30 carbon atoms,

The R is₁₉To R₂₁And may be substituted with at least one substituent independently selected from the group consisting of hydrogen, deuterium, carbamate, carboxyl, cyano, nitro, halogen, hydroxyl, carboxylate, alkyl of 1 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkynyl of 2 to 24 carbon atoms, cycloalkyl of 3 to 30 carbon atoms, heteroalkyl of 2 to 30 carbon atoms, aralkyl of 7 to 30 carbon atoms, aryl of 6 to 30 carbon atoms, heteroaryl of 2 to 30 carbon atoms, heteroaralkyl of 3 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, alkylamino of 1 to 30 carbon atoms, arylamino of 6 to 30 carbon atoms, aralkylamino of 6 to 30 carbon atoms, heteroarylamino of 2 to 24 carbon atoms, alkylsilyl of 1 to 30 carbon atoms, arylsilyl of 6 to 30 carbon atoms and aryloxy of 6 to 30 carbon atoms, when a plurality of the substituents are present, they are the same or different from each other.

In one embodiment of the present invention, when M is a functional group represented by chemical formula 5, ar is₃Ar and Ar₄A compound represented by any one of the following chemical formula 12 or chemical formula 13, which forms a ring by being connected to N of M.

Chemical formula 5

Chemical formula 12

Chemical formula 13

In the method, in the process of the invention,

X₈x is X₉Are identical or different from each other and are each independently selected from C (R₂₅)(R₂₆)、N(R₂₅) In the group consisting of C, N, O and S,

R₂₅r is R₂₆Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl of 2 to 24 carbon atoms, substituted or unsubstituted heteroalkyl of 2 to 30 carbon atoms, substituted or unsubstituted aralkyl of 7 to 30 carbon atoms, substituted or unsubstituted aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 2 to 30 carbon atoms, and substituted or unsubstituted C₆-C₃₀Heteroaralkyl, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and an arylsilyl group having 6 to 30 carbon atoms,

or said R₂₅To R₂₆Can also be selected from hydrogen, deuterium, carbamate, carboxyl, cyano, nitro, halogen, hydroxyl, carboxylate, alkyl with 1 to 30 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, cycloalkyl with 3 to 30 carbon atoms, heteroalkyl with 2 to 30 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 2 to 30 carbon atoms, heteroaralkyl with 3 to 30 carbon atoms, and heteroaralkyl with 1 to 30 carbon atoms 30, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, which are the same or different from each other when a plurality of the substituents are present.

In an example of the present invention, the compound represented by the chemical formula 2 represents a compound represented by the following chemical formula 14.

Chemical formula 14

In the method, in the process of the invention,

R₁to R₈，Ar₁To Ar₂L and L₂To L₃As defined in the invention claim 1.

In the organic electroluminescent device according to an embodiment of the present invention, L of formula 14₂L and L₃Are identical or different from one another and are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroarylene group having 6 to 30 nuclear atoms.

In one embodiment of the present invention, ar of formula 14₁Ar and Ar₂At least one of them represents a compound represented by the following chemical formula 15.

Chemical formula 15

In the method, in the process of the invention,

R₂₇to R₃₄Identical or different from each other, at least one of which is-L ₂-Ar₁and/or-L₃-Ar₂,

X is O or S, and the X is O or S,

in addition to-L₂-Ar₁and/or-L₃-Ar₂R outside₂₇To R₃₄Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl of 2 to 24 carbon atoms, substituted or unsubstituted heteroalkyl of 2 to 30 carbon atoms, substituted or unsubstituted aralkyl of 7 to 30 carbon atoms, substituted or unsubstituted aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 2 to 30 carbon atoms, and substituted or unsubstituted C₆-C₃₀Heteroaralkyl, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms and an arylsilyl group having 6 to 30 carbon atoms may form a saturated or unsaturated condensed ring together with the adjacent groups,

the R is₂₇To R₃₄And saturated or unsaturated condensed rings which they additionally form may be further substituted with at least one substituent independently selected from the group consisting of hydrogen, deuterium, urethane group, carboxyl group, cyano group, nitro group, halogen group, hydroxyl group, carboxylic ester group, alkyl group of 1 to 30 carbon atoms, alkenyl group of 2 to 30 carbon atoms, alkynyl group of 2 to 24 carbon atoms, cycloalkyl group of 3 to 30 carbon atoms, heteroalkyl group of 2 to 30 carbon atoms, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 2 to 30 carbon atoms, heteroaralkyl group of 3 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms, alkylamino group of 1 to 30 carbon atoms, arylamino group of 6 to 30 carbon atoms, heteroarylamino group of 2 to 24 carbon atoms, alkylsilyl group of 1 to 30 carbon atoms, arylsilyl group of 6 to 30 carbon atoms and aryloxy group of 6 to 30 carbon atoms, when plural said substituents exist, they are the same or different from each other.

In one example of the present invention, the chemical formula 15 represents compounds represented by the following chemical formulas 16 to 24.

Chemical formula 16

Chemical formula 17

Chemical formula 18

Chemical formula 19

Chemical formula 20

Chemical formula 21

Chemical formula 22

Chemical formula 23

Chemical formula 24

In the method, in the process of the invention,

x is O or S, and the X is O or S,

e is an integer of 0 to 6,

f is an integer of 0 to 6,

g is an integer of 0 to 4,

h is an integer of 0 to 4,

R₃₅to R₃₇Each of which is the same or different from the other and is independently selected from the group consisting of a single bond, hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl having 2 to 24 carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms, and substituted or unsubstituted C₆-C₃₀Heteroaralkyl, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and an arylsilyl group having 6 to 30 carbon atoms,

R₃₅to R₃₇Any one of which is combined with L₂Or L₃And (3) combining.

In one embodiment of the invention, the R₁₁To R₁₈Are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one example of the present invention, the compound represented by the chemical formula 1 is selected from the group consisting of:

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in one example of the present invention, the compound represented by the chemical formula 2 is selected from the group consisting of:

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according to an example of the present invention, the light emitting layer of the organic electroluminescent device of the present invention may include a dopant, which may include the compound represented by the chemical formula 1, and a host, which may include the compound represented by the chemical formula 2.

The organic compound represented by chemical formula 1 of the present invention may be used as a dopant substance, preferably, a material for blue dopant. In particular, the organic compound is a blue dopant species that shifts the emission wavelength to short wavelength sides above 7nm relative to existing blue dopants to provide a deep blue host/dopant system suitable for active matrix organic light emitting diodes (AM-OLEDs).

The organic compound represented by chemical formula 1 of the present invention prevents the generation of Excimer of dopant and increases the electron density of the Core and the stability of the dopant by introducing alkyl groups of the cyclic compound into the interior of pyrene molecular Core (Core), so that the efficiency and lifetime of the device are increased.

The organic compound represented by chemical formula 1 of the present invention has excellent solubility to a solution, thereby having characteristics of easy preparation of an organic electroluminescent device (OLED) by a solution process and reducing production costs.

An example of the present invention provides a material for forming a light emitting layer including an organic compound represented by chemical formula 1 and an organic compound represented by chemical formula 2. The material for forming the light emitting layer may include conventionally added substances, such as well-known dopants and host substances.

In an example of the present invention, the host substance may be an organic compound represented by the chemical formula 2, but is not limited to the example.

According to another example of the present invention, there is provided an organic electroluminescent device in which an organic thin film layer formed of a single layer or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode, the organic electroluminescent device characterized in that the light emitting layer includes an organic compound represented by the chemical formula 1 and a compound represented by the chemical formula 2.

In an example of the present invention, the organic electroluminescent device of the present invention may have a structure in which an anode (hole injection electrode), a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), and a cathode (electron injection electrode) are stacked in this order, and preferably, an Electron Blocking Layer (EBL) may be included between the anode and the emission layer, and an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) may be further included between the cathode and the emission layer. And, a Hole Blocking Layer (HBL) may be further included between the cathode and the light emitting layer. Hereinafter, the organic electroluminescent device of the present invention is exemplified. However, what is exemplified hereinafter is not intended to limit the organic electroluminescent device of the present invention.

In another example of the present invention, a method of manufacturing an organic electroluminescent device according to the present invention is provided, but what is exemplified hereinafter is not intended to limit the method of manufacturing an organic electroluminescent device of the present invention.

Specifically, first, an anode substance is applied on the surface of a substrate in a conventional manner to form an anode. In this case, the substrate used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling and water repellency. As the anode material, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin oxide (SnO) which is transparent and has excellent conductivity can be used ₂) Zinc oxide (ZnO), and the like.

Next, a Hole Injection Layer (HIL) material is vacuum thermally deposited or spin-coated on the anode surface in a conventional manner to form a hole injection layer. Examples of the hole injection layer material include copper phthalocyanine (CuPc), 4',4″ -tris (3-methylphenylamino) triphenylamine (m-MTDATA), 4',4″ -tris (3-methylphenylamino) phenoxybenzene (m-MTDAPB), 4',4″ -tris (N-carbazolyl) triphenylamine (TCTA) which is a dendritic (starburst) amine, 4',4″ -tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA), and IDE406 which is commercially available from japan light-emitting device (Idemitsu) corporation.

Vacuum thermal deposition or spin coating of a Hole Transport Layer (HTL) substance is performed on the hole injection layer surface in a conventional manner to form a hole transport layer. In this case, as the hole transport layer material, bis (N- (1-naphthyl-N-phenyl)) benzidine (. Alpha. -NPD), N '-bis (naphthalen-1-yl) -N, N' -biphenyl-benzidine (NPB), or N, N '-biphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (TPD) may be mentioned.

An emission layer (EML) material is vacuum thermally deposited or spin-coated on the surface of the hole transport layer in a conventional manner to form an emission layer. At this time, as a single light emitting substance or a light emitting host substance in the light emitting layer substance to be used, preferably, a compound represented by the chemical formula 2 may be used, but in the case of green, tris (8-hydroxyquinoline) aluminum (Alq ₃) Etc. in the case of blue, balq (8-hydroxyquinoline beryllium salt)) DPVBi (4, 4 '-bis (2, 2-biphenylvinyl) -1,1' -biphenyl) series, spirochete (Spiro) species, spiro-DPVBi (Spiro-4, 4 '-bis (2, 2-biphenylvinyl) -1,1' -biphenyl), liPBO (lithium 2- (2-benzoxazolyl) -phenolate), bis (biphenylvinyl) benzene, aluminum-quinoline metal complexes, imidazole, thiazole, and oxazole metal complexes, and the like.

In the light-emitting layer substance, in the case of a dopant that can be used together with the light-emitting host, as a blue fluorescent dopant, preferably, the organic compound represented by the chemical formula 1 of the present invention can be used, as other fluorescent dopants, IDE102, IDE105, available from japan light-emerging corporation (Idemitsu), tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3), iridium (III) bis [ (4, 6-difluorophenyl) pyridine-N, C-2' ] picolinate (FIrpic) (reference [ Chihaya Adachi et al., appl. Physis. Lett.,2001, 79, 3082-3084 ]), platinum (II) octaethylporphyrin (PtOEP), TBE002 (Corbion), and the like can be used as phosphorescent dopants.

Optionally, an Electron Blocking Layer (EBL) may also be formed between the hole transport layer and the light emitting layer.

An Electron Transport Layer (ETL) material is vacuum thermally deposited or spin-coated on the surface of the light emitting layer in a conventional manner to form an electron transport layer. In this case, in the case of using an electron transport layer substance, it is not particularly limited, and tris (8-hydroxyquinoline) aluminum (Alq₃)。

Alternatively, by further forming a Hole Blocking Layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant and a light emitting host together in the light emitting layer, a phenomenon in which triplet excitons or holes diffuse into the electron transport layer can be prevented. The phosphorescent dopant may be an organic compound represented by chemical formula 1, and the light emitting host may be an organic compound represented by chemical formula 2.

The formation of the hole blocking layer may be performed by vacuum thermal deposition and spin coating of a hole blocking layer substance in a conventional manner, and in the case of the hole blocking layer substance, there is no particular limitation, but preferably, (8-hydroxyquinoline) lithium (Liq), bis (8-hydroxy-2-methylhydroxyquinoline) -biphenol aluminum (BAlq), bathocuproine (BCP), liF, and the like may be used.

An Electron Injection Layer (EIL) substance is vacuum thermally deposited or spin-coated on the surface of the electron transport layer in a conventional manner to form an electron injection layer. In this case, as the electron injection layer material to be used, liF, liq, li can be used ₂O, baO, naCl, csF, etc.

And vacuum thermal deposition is carried out on the cathode substance on the surface of the electron injection layer in a conventional method to form a cathode. In this case, as the cathode material used, lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like can be used. Also, in the case of a front-surface light-emitting organic electroluminescent device, a transparent cathode that can transmit light may be formed by using Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO).

A coating layer (CPL) may be formed on the surface of the cathode by the composition for forming a coating layer of the present invention.

Effects of the invention

According to the present invention, there is provided an organic electroluminescent device comprising an organic compound which can sublimate and evaporate even at low temperature, realize a darker deep blue color, and can increase the efficiency and lifetime of the device.

Further, according to the present invention, there is provided an organic electroluminescent device comprising an organic compound which solves the productivity and cost problems inherent in the conventional blue dopant material process and which can easily realize a device in a solution process instead of a vapor deposition process which should be accompanied by the conventional organic electroluminescent device (OLED) process.

Further, according to the present invention, a Blue host/dopant system suitable for Deep Blue (Deep Blue) series of active matrix organic light emitting diodes (AM-OLED) is provided, and finally an organic electroluminescent device having characteristics of low driving voltage, high luminous efficiency, long lifetime, and the like is provided.

Drawings

FIG. 1 shows Nuclear Magnetic Resonance (NMR) data of intermediate 1-A compounds.

Detailed Description

The organic electroluminescent device comprises a first electrode, a second electrode, and at least one organic film between the first electrode and the second electrode,

the organic film includes at least one layer selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer,

the light emitting layer includes a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2,

chemical formula 1

In the method, in the process of the invention,

Chemical formula 2

In the method, in the process of the invention,

In addition to-L₂-Ar₁or-L₃-Ar₂R outside₁₁To R₂₀Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, and a substituted or unsubstituted alkynyl group having 2 to 30 carbon atomsA heteroalkyl group, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, and a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms,

the R is₁To R₈，L₂To L₃，Ar₁To Ar₂R is R₁₁To R₂₀And may also be composed of groups each independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxy, substituted or unsubstituted alkyl of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl of 2 to 24 carbon atoms, substituted or unsubstituted heteroalkyl of 2 to 30 carbon atoms, substituted or unsubstituted aralkyl of 7 to 30 carbon atoms, substituted or unsubstituted aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 2 to 30 carbon atoms, substituted or unsubstituted heteroaralkyl of 3 to 30 carbon atoms, substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, substituted or unsubstituted alkylamino of 1 to 30 carbon atoms, substituted or unsubstituted arylamino of 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino of 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino of 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl of 1 to 30 carbon atoms, and at least one of the same groups when they are present, or at least one of the substituted or unsubstituted silyl groups of carbon atoms and unsubstituted aryl groups of 6 to 30 carbon atoms.

Embodiments of the invention

The various embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art to which the present invention pertains, and the following embodiments may be modified into many different forms, and the scope of the present invention is not limited by the following embodiments. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the spirit of the invention to those skilled in the art.

Hereinafter, a method for synthesizing the compound represented by the chemical formula 1 will be described by way of a typical example. However, the synthetic methods of the plurality of compounds of the present invention are not limited to the methods exemplified below, and the plurality of compounds of the present invention may be prepared by the methods exemplified below and methods well known in the art.

Synthesis example

Synthesis of intermediate 1-A

After dissolving 288.4g (1 mol) of 2-methyl-4- (pyren-1-yl) butan-2-ol in 2.8L of Toluene (tolene), 10 weight percent (wt%) of acid is added. With the Dean-Stark (Dean-Stark) apparatus used to remove the moisture, stirring was performed for 12 hours under heating/refluxing conditions. After confirming that the reaction was completed, 10L of water was added to extract the toluene layer, and then the toluene layer was again extracted with 1L of water. With MgSO ₄The extracted solution was treated to remove residual moisture and dried in a vacuum oven. Then, column purification was performed with n-hexane to obtain 192.0g of compound a in a yield of 71%.

Synthesis example 1-1

Synthesis of Compound 1-1

4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ]]After pyrene and 8.02g (30 mmol) of N- (5- (tert-butyl) -2-methylphenyl) -2, 4-dimethylaniline were dissolved in 100ml of toluene, 5.76g (60.0 mmol) of NaOtBu, 0.46g (0.5 mmol) of Pd were added₂(dba)₃0.2g (1.0 mmol) of tBu₃P, stirring was performed for 6 hours in a heated/refluxed state. After confirming that the reaction was completed, 100ml of water was added to extract the toluene layer, and then 50ml of water was added again to re-extract the toluene layer. With MgSO₄Treated to remove residual moisture and dried in a vacuum oven. Then, n-hexane/dichloro was usedMethane (MC) was column purified to give `Compound 1-1` 5.06g in 60% yield.

MS(MALDI-TOF)m/z：843[M]+

Synthesis examples 1 to 2

Synthesis of Compounds 1-2

The compound 1-2'4.93g was obtained in 65% yield by the same method as in Synthesis example 1-1, except that 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 6.76g (30 mmol) of bis (2, 4-dimethylphenyl) amine were used instead of 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.02g (30 mmol) of N- (5- (tert-butyl) -2-methylphenyl) -2, 4-dimethylaniline.

MS(MALDI-TOF)m/z：759[M]+

Synthesis examples 1 to 3

Synthesis of Compounds 1-3

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.42g (10.0 mmol) of 1, 7-dibromo-5,5,9-trimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.02g (30 mmol) of N- (5- (tert-butyl) -2-methylphenyl) -2, 4-dimethylaniline, to obtain 'compound 1-3'5.05g in a yield of 62%.

MS(MALDI-TOF)m/z：815[M]+

Synthesis examples 1 to 4

Synthesis of Compounds 1-4

The reaction was conducted in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 7.60g (30 mmol) of 5- (tert-butyl) -2-methyl-N- (o-tolyl) aniline to obtain 'compound 1-4'4.64g in a yield of 57%.

MS(MALDI-TOF)m/z：815[M]+

Synthesis examples 1 to 5

Synthesis of Compounds 1-5

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.08g (30 mmol) of 2, 6-dimethyl-N- (4- (methyltrimethylsilyl) phenyl) aniline, to obtain 'compound 1-5'6.35g in 75% yield.

MS(MALDI-TOF)m/z：847[M]+

Synthesis examples 1 to 6

Synthesis of Compounds 1-6

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.42g (10.0 mmol) of 1, 7-dibromo-5,5,9-methyltrimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.02g (30 mmol) of 5- (tert-butyl) -N- (2, 5-dimethylphenyl) -2-methylaniline, to obtain 'compound 1-6'5.30g in a yield of 65%.

MS(MALDI-TOF)m/z：815[M]+

Synthesis examples 1 to 7

Synthesis of Compounds 1-7

Compounds '1 to 7'4.64g were obtained in 57% yield by performing the reaction in the same manner as in Synthesis example 1-1 except that 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 7.60g (30 mmol) of 4- (tert-butyl) -2, 6-dimethyl-N-phenylaniline were used.

MS(MALDI-TOF)m/z：815[M]+

Synthesis examples 1 to 8

Synthesis of Compounds 1-8

The reaction was conducted in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 7.60g (30 mmol) of N- (4- (tert-butyl) phenyl) -2, 6-dimethylaniline to obtain 'compound 1-8'4.97g in a yield of 61%.

MS(MALDI-TOF)m/z：815[M]+

Synthesis examples 1 to 9

Synthesis of Compounds 1-9

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.02g (30 mmol) of 5- (tert-butyl) -N- (2, 5-dimethylphenyl) -2-methylaniline to obtain 'compound 1-9'5.56g in a yield of 66%.

MS(MALDI-TOF)m/z：843[M]+

Synthesis examples 1 to 10

Synthesis of Compounds 1-10

The reaction was conducted in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 6.76g (30 mmol) of N- (3, 5-dimethylphenyl) -2, 6-dimethylaniline to obtain 'compound 1-10'4.48g in a yield of 59%.

MS(MALDI-TOF)m/z：759[M]+

Synthesis examples 1 to 11

Synthesis of Compounds 1-11

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.42g (10.0 mmol) of 1, 7-dibromo-5,5,9-methyltrimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 9.04g (30 mmol) of N- (4-isopropylphenyl) diphenyl [ b, d ] furan-3-amine, to obtain 'compound 1-11'5.74g in a yield of 65%.

MS(MALDI-TOF)m/z：883[M]+

Synthesis examples 1 to 12

Synthesis of Compounds 1-12

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 9.04g (30 mmol) of N- (4-isopropylphenyl) diphenyl [ b, d ] furan-3-amine, to obtain 'compound 1-12'6.38g in a yield of 70%.

MS(MALDI-TOF)m/z：911[M]+

Synthesis examples 1 to 13

Synthesis of Compounds 1-13

Compounds 1 to 13'5.09g were obtained in 52% yield by performing the reaction in the same manner as in Synthesis example 1-1 except that 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 9.46g (30 mmol) of N- ([ 1,1' -biphenyl ] -2-yl) diphenyl [ b, d ] furan-3-amine were used.

MS(MALDI-TOF)m/z：979[M]+

Synthesis examples 1 to 14

Synthesis of Compounds 1-14

Compounds 1 to 14'6.01g were obtained in 66% yield by performing the reaction in the same manner as in Synthesis example 1-1 except that 4.42g (10.0 mmol) of 1, 7-dibromo-5,5,9-methyltrimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 9.46g (30 mmol) of N- (4- (t-butyl) phenyl) diphenyl [ b, d ] furan-3-amine were used.

MS(MALDI-TOF)m/z：911[M]+

Synthesis examples 1 to 15

Synthesis of Compounds 1-15

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 9.04g (30 mmol) of N- (2-isopropylphenyl) diphenyl [ b, d ] furan-3-amine, to obtain 'compound 1-15'4.10g in a yield of 45%.

MS(MALDI-TOF)m/z：911[M]+

Synthesis examples 1 to 16

Synthesis of Compounds 1-16

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.32g (30 mmol) of N- (o-methylphenyl) diphenyl [ b, d ] furan-3-amine, to obtain 'compound 1-16'4.70g in a yield of 55%.

MS(MALDI-TOF)m/z：855[M]+

Synthesis examples 1 to 17

Synthesis of Compounds 1-17

By carrying out the reaction in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 5.08g (30 mmol) of diphenylamine, compound 1-17'4.98g was obtained in a yield of 77%.

MS(MALDI-TOF)m/z：646[M]+

Synthesis examples 1 to 18

Synthesis of Compounds 1-18

Compounds '1 to 18'4.74g were obtained in 66% yield by performing the same procedures as in Synthesis example 1-1 except that 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 6.16g (30 mmol) of bis (4-fluorophenyl) amine were used.

MS(MALDI-TOF)m/z：718[M]+

Synthesis examples 1 to 19

Synthesis of Compounds 1-19

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 9.64g (30 mmol) of bis ([ 1,1' -biphenyl ] -4-yl) amine, to obtain ' compound 1-19'5.99g in a yield of 63%.

MS(MALDI-TOF)m/z：951[M]+

Synthesis examples 1 to 20

Synthesis of Compounds 1-20

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.85g (30 mmol) of N- ([ 1,1' -biphenyl ] -4-yl) naphthalen-1-amine, to obtain ' compound 1-20'3.14g in a yield of 42%.

MS(MALDI-TOF)m/z：899[M]+

Synthesis examples 1 to 21

Synthesis of Compounds 1-21

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.26g (30 mmol) of N-benzodibenzo [ b, d ] thiophen-4-amine, to obtain 'compound 1-21'5.50g in a yield of 64%.

MS(MALDI-TOF)m/z：859[M]+

Synthesis examples 1 to 22

Synthesis of Compounds 1-22

By carrying out the reaction in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 5.11g (30 mmol) of N-phenylpyridin-3-amine, compound 1-22'2.14g was obtained in a yield of 33%.

MS(MALDI-TOF)m/z：648[M]+

Synthesis examples 1 to 23

Synthesis of Compounds 1-23

Compounds 1 to 23'3.52g were obtained in 45% yield by performing the reaction in the same manner as in Synthesis example 1-1 except that 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 7.12g (30 mmol) of N-phenyl-4- (trifluoromethyl) aniline were used.

MS(MALDI-TOF)m/z：782[M]+

Synthesis examples 1 to 24

Synthesis of Compounds 1-24

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 8.56g (30 mmol) of 9, 9-dimethyl-N-phenyl-9H-fluoren-1-amine, to obtain 'compound 1-24'5.28g in a yield of 60%.

MS(MALDI-TOF)m/z：879[M]+

Synthesis examples 1 to 25

Synthesis of Compounds 1-25

By carrying out the reaction in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 6.88g (30 mmol) of bis (4-methoxyphenyl) amine, compound 1-25'5.45g was obtained in a yield of 71%.

MS(MALDI-TOF)m/z：766[M]+

Synthesis examples 1 to 26

Synthesis of Compounds 1-76

Compounds '1 to 76'4.85g were obtained in 71% yield by performing the reaction in the same manner as in Synthesis example 1-1 except that 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 5.91g (30 mmol) of 2, 6-dimethyl-N-aniline were used.

MS(MALDI-TOF)m/z：702[M]+

Synthesis examples 1 to 27

Synthesis of Compounds 1-77

The reaction was carried out in the same manner as in Synthesis example 1-1 except for using 4.70g (10.0 mmol) of 1, 7-dibromo-9-isopropyl-5, 5-dimethyl-4, 5-dihydro-3H-benzo [ cd ] pyrene and 5.91g (30 mmol) of 2, 6-dimethyl-N- (o-tolyl) amine, to obtain 'Compound 1-77'4.67g in a yield of 64%.

MS(MALDI-TOF)m/z：731[M]+

Synthesis example 2-1

Synthesis of Compound 2-1

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and dibenzofuran-4-boronic acid (2.33 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.45g (63%) of compound 2-1 was obtained.

MS(MALDI-TOF)m/z：420[M]+

Synthesis example 2-2

Synthesis of Compound 2-2

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and dibenzofuran-3-boronic acid (2.33 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.81g (67%) of compound 2-2 was obtained.

MS(MALDI-TOF)m/z：420[M]+

Synthesis examples 2 to 3

Synthesis of Compound 2-3

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and dibenzofuran-2-boronic acid (2.33 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.73g (65%) of compound 2-3 was obtained.

MS(MALDI-TOF)m/z：420[M]+

Synthesis examples 2 to 4

Synthesis of Compounds 2-4

/>

9-bromo-10-phenylanthracene (33.3 g,10 mmol) and dibenzofuran-1-boronic acid (2.33 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.77g (66%) of compound 2-4 was obtained.

MS(MALDI-TOF)m/z：420[M]+

Synthesis examples 2 to 5

Synthesis of Compounds 2-5

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and dibenzofuran-6-phenyl-4-boronic acid (3.16 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, it was recrystallized from toluene and n-heptane, to obtain 2.58g (52%) of compound 2-5.

MS(MALDI-TOF)m/z：496[M]+

Synthesis examples 2 to 6

Synthesis of Compounds 2-6

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and dibenzofuran-7-phenyl-4-boronic acid (3.16 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, it was recrystallized from toluene and n-heptane, whereby 2.33g (47%) of the compound 2-6 was obtained.

MS(MALDI-TOF)m/z：496[M]+

Synthesis examples 2 to 7

Synthesis of Compounds 2-37

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and naphtho [2,3-b ] benzofuran-3-yl-boronic acid (2.88 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, and water, it was recrystallized from toluene to obtain 2.49g (53%) of compound 2-37.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 8

Synthesis of Compounds 2-38

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and naphtho [1,2-b ] benzofuran-9-yl-boronic acid (2.88 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, and water, it was recrystallized from toluene to obtain 2.49g (53%) of compound 2-38.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 9

Synthesis of Compound 2-39

9-bromo-10-phenylanthracene (3.33 g,10 mmol) and 2- (dinaphtho [2,1-b:1',2' -d ] furan-5-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan (4.73 g,12 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, and water, it was recrystallized from toluene to obtain 2.81g (54%) of compound 2-39.

MS(MALDI-TOF)m/z：520[M]+

Synthesis examples 2 to 10

Synthesis of Compound 2-61

10-bromo-9- (naphthalen-1' -yl) anthracene (3.83 g,10.0 mmol) and dibenzofuran-4-boronic acid (2.34 g,11 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. 0.231g (0.2 mmol) of tetrakis (triphenylphosphine) palladium was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 3.20g (37%) of compound 2-61 was obtained.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 11

Synthesis of Compound 2-62

10-bromo-9- (naphthalen-2' -yl) anthracene (3.83 g,10.0 mmol) and dibenzofuran-4-boronic acid (2.34 g,11 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. 0.231g (0.2 mmol) of tetrakis (triphenylphosphine) palladium was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resulting solid with toluene, methanol, water, and recrystallized in toluene, 4.79g (55%) of compound 2-62 was obtained.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 12

Synthesis of Compounds 2-66

4- (10-Bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4- (naphthalene-1-Phenyl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature and water was added thereto, the layers were separated, and the organic layer was separated with MgSO₄Treated to remove moisture. After filtration, the filtrate was concentrated under reduced pressure, and recrystallized from methylene chloride and n-heptane to obtain 1.85g (34%) of compound 2-66.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 13

Synthesis of Compound 2-67

4- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4- (naphthalen-2-yl) phenyl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 3.06g (56%) of compound 2-67 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 14

Synthesis of Compound 2-73

4- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4-phenylnaphthalen-1-yl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.67g (49%) of compound 2-73 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 15

Synthesis of Compound 2-75

4- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (6-phenylnaphthalen-2-yl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 3.06g (56%) of compound 2-75 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 16

Synthesis of Compound 2-78

10-bromo-9- (naphthalen-1' -yl) anthracene (3.83 g,10.0 mmol) and dibenzofuran-3-boronic acid (2.34 g,11 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. 0.231g (0.2 mmol) of tetrakis (triphenylphosphine) palladium was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.49g (53%) of compound 2-78 was obtained.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 17

Synthesis of Compound 2-79

10-bromo-9- (naphthalen-2' -yl) anthracene (3.83 g,10.0 mmol) and dibenzofuran-3-boronic acid (2.34 g,11 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. 0.231g (0.2 mmol) of tetrakis (triphenylphosphine) palladium was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.02g (43%) of compound 2-79 was obtained.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 18

Synthesis of Compound 2-83

3- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4- (naphthalen-1-yl) phenyl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature and water was added thereto, followed by layer separation, and the organic layer was separated with MgSO₄Treated to remove moisture. After filtration, the filtrate was concentrated under reduced pressure, and recrystallized from methylene chloride and n-heptane, 1.37g (25%) of compound 2-83 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 19

Synthesis of Compounds 2-84

3- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4- (naphthalen-2-yl) phenyl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 3.06g (56%) of compound 2-84 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 20

Synthesis of Compounds 2-90

3- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4-phenylnaphthalen-1-yl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resulting solid with toluene, methanol, water, and recrystallized in toluene, 2.40g (44%) of compound 2-90 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 21

Synthesis of Compound 2-92

3- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (6-phenylnaphthalen-2-yl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 2.30g (42%) of compound 2-92 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 22

Synthesis of Compounds 2-95

10-bromo-9- (naphthalen-1' -yl) anthracene (3.83 g,10.0 mmol) and dibenzofuran-2-boronic acid (2.34 g,11 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.2 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resulting solid with toluene, methanol, water, and recrystallized in toluene, 2.54g (54%) of compound 2-95 was obtained.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 23

Synthesis of Compounds 2-96

10-bromo-9- (naphthalen-2' -yl) anthracene (3.83 g,10.0 mmol) and dibenzofuran-2-boronic acid (2.34 g,11 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. 0.231g (0.2 mmol) of tetrakis (triphenylphosphine) palladium was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resulting solid with toluene, methanol, water, and recrystallized in toluene, 2.54g (54%) of compound 2-96 was obtained.

MS(MALDI-TOF)m/z：470[M]+

Synthesis examples 2 to 24

Synthesis of Compounds 2-100

2- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4- (naphthalen-1-yl) phenyl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature and water was added thereto, followed by layer separation, and the organic layer was separated with MgSO₄Treated to remove moisture. After filtration, the filtrate was concentrated under reduced pressure and recrystallized from methylene chloride and n-heptane to obtain1.27g (22%) of Compound 2-100.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 25

Synthesis of Compounds 2-101

2- (10-bromoanthracene-9-yl) dibenzofuran (4.23 g,10.0 mmol) and (4- (naphthalen-2-yl) phenyl) boronic acid (2.72 g,11.0 mmol), potassium carbonate (5.16 g,20 mmol), toluene 100mL, water 20mL, ethanol 100mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, water, and recrystallized in toluene, 3.17g (55%) of compound 2-101 was obtained.

MS(MALDI-TOF)m/z：546[M]+

Synthesis examples 2 to 26

Synthesis of Compounds 2-142

9-bromo-10- (4- (naphthalen-1-yl) phenyl) anthracene (4.59 g,10 mmol) and 2- (dinaphtho [2,1-b:1',2' -d ] furan-5-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan (4.73 g,12 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, and water, it was recrystallized from toluene to obtain 3.74g (58%) of compound 2-142.

MS(MALDI-TOF)m/z：646[M]+

Synthesis examples 2 to 27

Synthesis of Compound 2-191

10-bromo-9- (naphthalen-1' -yl) anthracene (3.83 g,10.0 mmol) and naphtho [2,3-b ] benzofuran-3-yl-boronic acid (2.88 g,11 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, and water, it was recrystallized from toluene to obtain 3.17g (61%) of compound 2-191.

MS(MALDI-TOF)m/z：520[M]+

Synthesis examples 2 to 28

Synthesis of Compound 2-193

9- ([ 1,1' -biphenyl ] -4-yl) -10-bromoanthracene (4.09 g,10 mmol) and 2- (dinaphtho [2,1-b:1',2' -d ] furan-5-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan (4.73 g,12 mmol), potassium carbonate (2.76 g,20 mmol), toluene 50mL, water 10mL, ethanol 10mL were added. Tetrakis (triphenylphosphine) palladium (0.231 g,0.20 mmol) was charged and refluxed for 10 hours. After this time, the reaction mixture was cooled to room temperature, and after washing the resultant solid with toluene, methanol, and water, it was recrystallized from toluene to obtain 3.28g (55%) of compound 2-193.

MS(MALDI-TOF)m/z：596[M]+

Comparative Synthesis example 1

Synthesis of Compound 1-A

3.86g of Compound 1-A was obtained in a yield of 72% by performing the reaction in the same manner as in Synthesis example 1-1 except that 3.60g (10.0 mmol) of 1, 6-dibromopyrene and 5.08g (30 mmol) of diphenylamine were used.

MS(MALDI-TOF)m/z：536[M]+

Comparative Synthesis example 2

Synthesis of Compound 1-B

4.76g of Compound 1-B was obtained in a yield of 65% by performing the reaction in the same manner as in Synthesis example 1-1 except that 3.60g (10.0 mmol) of 1, 6-dibromopyrene and 8.02g (30 mmol) of 5- (tert-butyl) -N- (2, 5-dimethylphenyl) -2-methylaniline were used.

MS(MALDI-TOF)m/z：733[M]+

Comparative Synthesis example 3

4.73g of Compound 1-C was obtained in a yield of 60% by performing the same manner as in Synthesis example 1-1 except that 4.16g (10.0 mmol) of 1, 6-dibromo-3, 8-diethyl pyrene and 8.02g (30 mmol) of 5- (tert-butyl) -N- (2, 5-dimethylphenyl) -2-methylaniline were used.

MS(MALDI-TOF)m/z：789[M]+

Examples: thin film Procedural Language (PL) data measurement

PL was measured in a thin film state after vapor deposition of the following compound 2-B, compound 2-C, or the compound 2-62 as a main body on an Indium Tin Oxide (ITO) thin film and formation of a light-emitting layer by doping 3% of the compound 1-B or the compound 1-7 of the present invention.

Compound 2-B, compound 2-C

TABLE 1

As a result of measuring the wavelength in this case, it was confirmed that there was no wavelength change even when the compound having a polar substituent introduced was used as a host in the case of using the dopant of the present invention, since the compound having no polar substituent and the compound having a polar substituent introduced were used as a host in the case of using the dopant of the present invention.

In contrast, in the case of using a conventional dopant and a compound having a polar substituent introduced therein as a host, the shift to a long wavelength (red direction) was confirmed.

Example 1: preparation of organic electroluminescent device

A substrate in which an Ag alloy as a light reflecting layer and Indium Tin Oxide (ITO) (10 nm) as an anode of an organic electroluminescent device were sequentially laminated was divided into a cathode region and an anode region and an insulating layer by a photolithography process (Photo-lithography), and Patterning was performed, after which ultraviolet Ozone (UV Ozone) treatment and surface treatment by O2: N2 plasma were performed for the purpose of increasing work-function (work-function) and removing slag (descum) of the anode (indium tin oxide). Thereon, 1,4,5,8,9,11-hexaazabenzonitrile (HAT-CN) is formed by a Hole Injection Layer (HIL)

Thickness. Next, by reacting N4, N4, N4', N4' -tetrakis ([ 1,1' -biphenyl)]-4-yl) - [1,1' -biphenyl]-4,4' -diamine being vacuum evaporated to form +_ on top of said hole injection layer>

A hole transport layer of thickness. In the upper part of the Hole Transport Layer (HTL) in +.>

Thickness formation of N-phenyl-N- (4- (spiro [ benzo [ de ])]Anthracene-7, 9' -fluorene]-2' -yl) phenyl) diphenyl [ b, d]Furan-4-amine was used as an Electron Blocking Layer (EBL) on top of which a >

The light emitting layer (EML) of thickness serves as the host for the Blue (Blue) light emitting layer.

Above this, 2- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ] is mixed in a weight ratio of 1:1]Imidazole and lithium (8-hydroxyquinoline) (LiQ) in the form of

An Electron Transport Layer (ETL) was deposited in thickness, and magnesium (Mg) and silver (Ag) were added in a 9:1 ratio as a cathode>

And (5) evaporating the thickness. And on the cathode, N4' -diphenyl-N4, N4' -bis (4- (9-phenyl-9H-carbazol-3-yl) phenyl) - [1,1' -biphenyl]The 4,4' -diamine was vapor deposited at a thickness of 63 to 65nm as a coating layer (CPL). Protection of organic electroluminescent devices from atmospheric O by fitting sealing caps (seal caps) with UV-curable glue on a cover layer (CPL)₂Or the influence of moisture, thereby producing an organic electroluminescent device.

Examples 2 to 36: preparation of organic electroluminescent device

An organic electroluminescent device was prepared by the same method as in example 1, except that the compounds shown in table 4 below were used as dopants instead of the compound 1-1, and the doping amounts of the dopants were adjusted.

Comparative examples 1 to 3: preparation of organic electroluminescent device

An organic electroluminescent device was manufactured by the same method as in example 1, except that the compounds 1-a to 1-C were used as a dopant instead of the compound 1.

Comparative examples 4 to 5: preparation of organic electroluminescent device

An organic electroluminescent device was prepared by the same method as in example 1, except that the following compounds 2-a to 2-B were used as a host instead of the compound 2.

Compound 2-A, compound 2-B, compound 2-C

Experimental example 1: analysis of characteristics of organic electroluminescent devices

The organic electroluminescent devices prepared in examples 1 to 9 and comparative example 1 were used at 1000cd/m as follows²The characteristics were compared in terms of brightness and the results thereof are shown in table 2 below.

TABLE 2

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Referring to the table 2, in the case of the organic electroluminescent device according to the present invention, it was confirmed that the driving voltage (Volt) exhibited equal or less (low driving voltage) when compared with the comparative example, and the light emitting efficiency (Cd/a) was improved.

Industrial applicability

Claims

1. An organic electroluminescent device comprising a first electrode, a second electrode and at least one organic film between the first electrode and the second electrode, characterized in that,

the light emitting layer includes a compound represented by the following chemical formula 3 and a compound represented by the following chemical formula 14,

chemical formula 3:

in the method, in the process of the invention,

R₉r is R₁₀Are the same or different from each other and are each independently selected from the group consisting of hydrogen, an unsubstituted alkyl group having 1 to 10 carbon atoms, an unsubstituted cycloalkyl group having 3 to 12 carbon atoms, an unsubstituted alkoxy group having 1 to 10 carbon atoms, halogen, cyano group, an unsubstituted alkylsilyl group having 1 to 30 carbon atoms and an arylsilyl group having 6 to 30 carbon atoms,

the R is₉R is R₁₀Can also be substituted with at least one substituent independently selected from the group consisting of hydrogen, deuterium, urethane groups, carboxyl groups, cyano groups, nitro groups, halogen groups, hydroxyl groups, carboxylic acid ester groups, alkyl groups of 1 to 30 carbon atoms, alkenyl groups of 2 to 30 carbon atoms, alkynyl groups of 2 to 24 carbon atoms, cycloalkyl groups of 3 to 30 carbon atoms, and heteroalkyl groups of 2 to 30 carbon atoms, respectively, when a plurality of the substituents are present, they are the same as or different from each other,

n is an integer of 2 and is a number,

R₁、R₃to R₆And R is₈Are the same or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, an unsubstituted alkyl group having 1 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 30 carbon atoms, an unsubstituted alkynyl group having 2 to 30 carbon atoms, an unsubstituted cycloalkyl group having 3 to 30 carbon atoms, an unsubstituted heteroalkyl group having 2 to 30 carbon atoms and an unsubstituted alkylsilyl group having 1 to 30 carbon atoms,

R₂and R is₇Is prepared from the following chemical componentsA functional group represented by the formula 4,

chemical formula 4:

chemical formula 5:

in the method, in the process of the invention,

l is a single bond,

m is a functional group represented by the chemical formula 5,

Ar₃ar and Ar₄Each independently selected from the group consisting of an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 2 to 30 carbon atoms,

the Ar is as follows₃Ar and Ar₄It is also possible to substitute at least one substituent independently selected from the group consisting of hydrogen, deuterium, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroaralkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, when a plurality of the substituents are present, they are the same or different from each other,

Chemical formula 14:

in the method, in the process of the invention,

L₂l and L₃Is a single bond,

Ar₁ar and Ar₂Are identical or different from each other and are each independently selected from the group consisting of unsubstituted carbon atoms6 to 30 aryl groups, unsubstituted heteroaryl groups having 3 to 30 carbon atoms,

the Ar is as follows₁Ar and Ar₂At least one of which is a compound represented by the following chemical formulas 16 to 24,

chemical formula 16:

chemical formula 17:

chemical formula 18:

chemical formula 19:

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chemical formula 20:

chemical formula 21:

chemical formula 22:

chemical formula 23:

chemical formula 24:

in the method, in the process of the invention,

x is O, and the oxygen content of the catalyst is equal to or higher than that of the catalyst,

e is an integer of 0 to 6,

f is an integer of 0 to 6,

g is an integer of 0 to 4,

h is an integer of 0 to 4,

R₃₅to R₃₇Each of which is the same or different from the other, is independently selected from the group consisting of a single bond, hydrogen, deuterium, an unsubstituted alkyl group having 1 to 30 carbon atoms, an unsubstituted cycloalkyl group having 3 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 30 carbon atoms, an unsubstituted alkynyl group having 2 to 24 carbon atoms, an unsubstituted heteroalkyl group having 2 to 30 carbon atoms and an unsubstituted alkylsilyl group having 1 to 30 carbon atoms, R₃₅To R₃₇Any one of which is combined with L₂Or L₃In combination with the combination of the two,

R₁₁to R₁₈Are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, an unsubstituted alkyl group having 1 to 30 carbon atoms, an unsubstituted cycloalkyl group having 3 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 30 carbon atoms, an unsubstituted alkynyl group having 2 to 24 carbon atoms, and an unsubstituted heteroalkyl group having 2 to 30 carbon atoms,

The Ar is as follows₁To Ar₂It is also possible to form a group consisting of an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an heteroalkyl group having 2 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an heteroaralkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, an heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms which are independently selected from hydrogen, deuterium, an aralkylyl group having 3 to 30 carbon atoms, an alkylamino group having 6 to 30 carbon atoms, an aralkylamino group having 2 to 24 carbon atomsIs substituted by at least one substituent, and when a plurality of said substituents are present, they are the same or different from each other.

2. The organic electroluminescent device of claim 1, wherein the Ar ₃Ar and Ar₄Is a substituent selected from the group consisting of compounds represented by the following chemical formulas 6 to 11,

chemical formula 6:

chemical formula 7:

chemical formula 8:

chemical formula 9:

chemical formula 10:

chemical formula 11:

in the method, in the process of the invention,

* In order to form part of the bond,

p is an integer of 0 to 4,

q is an integer of 0 to 3,

X₁selected from C (R)₂₃) In the group consisting of N, S and O,

The R is₂₁To R₂₄It is also possible to substitute at least one substituent independently selected from the group consisting of hydrogen, deuterium, carbamate, carboxyl, cyano, nitro, halogen, hydroxyl, carboxylate, alkyl of 1 to 30 carbon atoms, alkenyl of 2 to 30 carbon atoms, alkynyl of 2 to 24 carbon atoms, cycloalkyl of 3 to 30 carbon atoms, heteroalkyl of 2 to 30 carbon atoms, aralkyl of 7 to 30 carbon atoms, aryl of 6 to 30 carbon atoms, heteroaryl of 2 to 30 carbon atoms, heteroaralkyl of 3 to 30 carbon atoms, alkoxy of 1 to 30 carbon atoms, alkylamino of 1 to 30 carbon atoms, arylamino of 6 to 30 carbon atoms, aralkylamino of 6 to 30 carbon atoms, heteroarylamino of 2 to 24 carbon atoms, alkylsilyl of 1 to 30 carbon atoms, arylsilyl of 6 to 30 carbon atoms and aryloxy of 6 to 30 carbon atoms, when a plurality of the substituents are present, they are the same or different from each other.

3. The organic electroluminescent device of claim 1, wherein R₁₁To R₁₈Are the same or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, an unsubstituted alkyl group having 1 to 30 carbon atoms, and an unsubstituted cycloalkyl group having 3 to 30 carbon atoms.

4. The organic electroluminescent device according to claim 1, wherein the compound represented by chemical formula 3 is selected from the group consisting of:

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5. the organic electroluminescent device according to claim 1, wherein the compound represented by chemical formula 14 is selected from the group consisting of: