CN105745301B - Novel light-emitting compound and organic light-emitting element comprising same - Google Patents
Novel light-emitting compound and organic light-emitting element comprising same Download PDFInfo
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Abstract
The organic light-emitting compound of the present invention has excellent charge transfer characteristics, high triplet energy, and high Tg, and therefore, when applied to an organic light-emitting device, the organic light-emitting compound can have a low driving voltage, high efficiency, low power consumption, and a long lifetime.
Description
Technical Field
The present invention relates to a novel light-emitting compound and an organic light-emitting element including the same.
Background
Recently, a self-luminous organic light emitting element which can be driven at a low voltage has been attracting attention as a next-generation display element because it is superior in viewing angle, contrast, and the like, does not require a backlight, is lightweight and thin, is advantageous in power consumption, and has a wide color reproduction range, as compared with a Liquid Crystal Display (LCD) which is a mainstream of a flat panel display element.
Materials used as an organic layer in an organic light emitting element are broadly classified by function into a light emitting material, a hole injecting material, a hole transporting material, an electron injecting material, and the like. The light-emitting materials may be classified into high-molecular and low-molecular materials according to molecular weight, fluorescent materials from a singlet excited state of electrons and phosphorescent materials from a triplet excited state of electrons according to a light-emitting mechanism, and the light-emitting materials may be classified into blue, green and red light-emitting materials according to light-emitting colors and yellow and orange light-emitting materials required for exhibiting better natural colors. In addition, in order to increase the light emitting efficiency by increase in color purity and energy transfer, a host/dopant system may be used as the light emitting substance. The principle is as follows: when a small amount of a dopant having a smaller energy band gap and superior light emission efficiency than that of a host mainly constituting the light emitting layer is mixed in the light emitting layer, excitons generated in the host are transferred to the dopant to emit light with high efficiency. In this case, since the wavelength of the host shifts to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of the dopant and the host used.
Many compounds have been known as materials for such organic light emitting elements, but in the case of organic light emitting elements using conventionally known materials, there are many difficulties in practical use due to high driving voltage, low efficiency, and short lifetime. Therefore, efforts are being made to develop an organic light emitting element having low voltage driving, high luminance, and long life using a substance having excellent characteristics.
Disclosure of Invention
In order to solve the above-described problems, an object of the present invention is to provide a novel light-emitting compound which has excellent charge transfer characteristics, high triplet energy, and high Tg, and which can have a low driving voltage, high efficiency, low power consumption, and a long life when applied to an organic light-emitting element.
It is another object of the present invention to provide an organic light-emitting element which can realize a low driving voltage, high efficiency, low power consumption, and a long life by including the above compound.
In order to achieve the above object, the present invention provides a light emitting compound represented by the following chemical formula 1:
[ chemical formula 1]
In the above-mentioned formula, the compound of formula,
each X is independently CR0Or N, R0Is hydrogen; deuterium; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30Aryl of (a); or C substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30The heteroaryl group of (a) is a group,
y is C or Si, and Y is C or Si,
R1is hydrogen; deuterium; by deuterium, halogen,Amino, nitrile, nitro or unsubstituted C1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C6-50Aryl of (a); or by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C2-50The heteroaryl group of (a) is a group,
R2、R3、R4and R5Each independently is hydrogen; deuterium; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C6-50Aryl of (a); or by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C2-50Heteroaryl of (A), R4And R5A loop may be selectively formed.
In addition, the present invention provides an organic light emitting element including the compound represented by the above chemical formula 1 as a light emitting substance in an organic layer.
The light-emitting compound of the present invention has excellent charge transfer characteristics, high triplet energy, and high Tg, and therefore, when applied to an organic light-emitting element, the light-emitting compound can have a low driving voltage, high efficiency, low power consumption, and a long lifetime.
Drawings
Fig. 1 schematically shows a cross-section of an OLED according to one embodiment of the invention.
Reference symbols of the drawings
10: substrate
11: anode
12: hole injection layer
13: hole transport layer
14: luminescent layer
15: electron transport layer
16: cathode electrode
Detailed Description
The compound of the present invention is characterized by being represented by the following chemical formula 1.
[ chemical formula 1]
In the above-mentioned formula, the compound of formula,
each X is independently CR0Or N, R0Is hydrogen; deuterium; substituted or not by deuterium, halogen, amino, nitrile, nitroSubstituted C1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30Aryl of (a); or C substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30The heteroaryl group of (a) is a group,
y is C or Si, and Y is C or Si,
R1is hydrogen; deuterium; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C6-50Aryl of (a); or by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C2-50The heteroaryl group of (a) is a group,
R2、R3、R4and R5Each independently is hydrogen; deuterium; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkyl groups of (a); substituted or not by deuterium, halogen, amino, nitrile, nitro radicalsSubstituted C2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C6-50Aryl of (a); or by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C2-50Heteroaryl of (A), R4And R5A loop may be selectively formed.
In the present invention, the compound represented by the above chemical formula 1 is preferably one of the following structures.
In the above structure, X, R4And R5The same as defined in chemical formula 1.
Z is CR8Or N, R8Is hydrogen; deuterium; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30Aryl of (a); or by deuterium, halogen,Amino, nitrile, nitro or unsubstituted C2-30The heteroaryl group of (a) is a group,
a is O, S, Se, TE, N-Ar1Wherein Ar is1Is hydrogen; deuterium; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30An aryloxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30Aryl of (a); or C substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30The heteroaryl group of (a) is a group,
ar is independently deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C6-38Aryl of (a); or by deuterium, halogen, amino, nitrile, nitro, C1-30Alkyl of (C)2-30Alkenyl of, C2-30Alkynyl of (A), C1-30Alkoxy group of (C)6-30Aryloxy group of (A), C6-30Aryl or C of2-30Heteroaryl substituted or unsubstituted C2-38The heteroaryl group of (a) is a group,
R6and R7Each independently is hydrogen; deuterium; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkyl groups of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkenyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30Alkynyl of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro1-30Alkoxy group of (a); c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30Of (a) aryloxyA group; c substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro6-30Aryl of (a); or C substituted or unsubstituted by deuterium, halogen, amino, nitrile, nitro2-30The heteroaryl group of (a) is a group,
n is an integer of 2 to 6.
In the present invention, preferable examples of the compound represented by the above chemical formula 1 are as follows:
the compound of chemical formula 1 according to the present invention has excellent charge transfer characteristics and high triplet energy and Tg, and thus can have low driving voltage, high efficiency, low power consumption, and long life when applied to an organic light emitting device.
Further, the present invention provides a method for producing chemical formula 1, comprising the steps of reaction formula 1:
[ reaction formula 1]
Specific examples of the reaction formula 1 include the following reaction formula 1-1.
[ reaction formula 1-1]
In the above reaction formula, X, Y, Ar, R1、R2、R3、R4And R5Respectively, as defined above.
In addition, the present invention provides an organic light emitting element including the compound represented by the above chemical formula 1 as a light emitting substance in an organic layer. In this case, the compound of the present invention may be used alone or together with a known organic light emitting compound.
The organic light-emitting device of the present invention includes 1 or more organic layers containing the compound represented by chemical formula 1, and the method for manufacturing the organic light-emitting device is described below.
The organic light emitting device may include one or more organic layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL) between an anode (anode) and a cathode (cathode).
First, an anode electrode substance having a high work function is deposited on the substrate to form an anode. In this case, the substrate used in a general organic light-emitting device can be used, and in particular, a glass substrate or a transparent plastic substrate excellent in mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance is preferably used. In addition, the material is used as an anode electrodeAs the material, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin oxide (SnO), which are transparent and excellent in conductivity, can be used2) Zinc oxide (ZnO), and the like. The substance for an anode electrode can be deposited by a general anode formation method, specifically, by a deposition method or a sputtering method.
Next, a hole injection layer material may be formed on the anode electrode by a method such as a vacuum deposition method, a spin coating method, a casting method, or an LB (Langmuir-blodgett, Langmuir blodgett) method, but a uniform film material is easily obtained and pinholes are less likely to occur
And the like, it is preferably formed by a vacuum vapor deposition method. When the hole injection layer is formed by the vacuum deposition method, the deposition conditions are different depending on the compound used as the material of the hole injection layer, the structure and thermal characteristics of the target hole injection layer, and the like, but it is generally preferable to set the deposition temperature to 50 to 500 ℃ and the deposition temperature to 10 ℃-8To 10-3Vacuum degree of torr (torr) of 0.01 to
The deposition rate of,
The layer thickness is suitably selected within the range of 5 μm.
The hole injection layer material is not particularly limited, and a phthalocyanine compound such as copper phthalocyanine or star amine disclosed in U.S. Pat. No. 4,356,429, or the like can be used
Derivatives such as TCTA (4,4' -tris (N-carbazolyl) triphenylamine), m-MTDATA (4,4' -tris (3-methylphenylamino) triphenylamine), m-MTDAPB (4,4' -tris (3-methylphenylamino) phenoxybenzene), HI-406 (N-carbazolyl) triphenylamine, and mixtures thereof1,N1'- (biphenyl-4, 4' -diyl) bis (N)1- (Naphthalen-1-yl) -N4,N4Diphenylbenzene-1, 4-diamine), etc. as a hole injection layer material.
Next, the hole transport layer material may be formed on the hole injection layer by a method such as vacuum deposition, spin coating, casting, or LB method, but it is preferably formed by vacuum deposition in view of easy availability of uniform film quality and less occurrence of pinholes. In the case of forming the hole transport layer by the vacuum evaporation method, the evaporation conditions are different depending on the compound used, but it is generally preferable to select the conditions within the range substantially the same as the conditions for forming the hole injection layer.
Specifically, the hole transport layer material may be a carbazole derivative such as N-phenylcarbazole or polyvinylcarbazole, or a general amine derivative having an aromatic condensed ring such as N, N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1, 1-biphenyl ] -4,4' -diamine (TPD) or N, N ' -bis (naphthalene-1-yl) -N, N ' -diphenylbenzidine (α -NPD).
Thereafter, a light-emitting layer material may be formed on the hole transport layer by a method such as vacuum deposition, spin coating, casting, or LB method, but it is preferable to form the light-emitting layer material by vacuum deposition because uniform film quality is easily obtained and pinholes are not easily generated. In the case of forming the light-emitting layer by the vacuum vapor deposition method, the vapor deposition conditions are different depending on the compound used, but are preferably selected within the range of conditions almost the same as those for forming the hole injection layer. In addition, the light emitting layer material may use the compound represented by chemical formula 1 of the present invention as a host or a dopant.
When the compound represented by chemical formula 1 is used as a light-emitting host, a light-emitting layer can be formed using a phosphorescent or fluorescent dopant. In this case, as the fluorescent dopant, IDE102, IDE105 or BD142 (N) available from yohimoto corporation (Idemitsu corporation) can be used6,N12-bis (3, 4-dimethylphenyl) -N6,N12-two
Base of
6, 12-diamine) which, as phosphorescent dopant, can be co-vacuum evaporated (doped) with a green phosphorescent dopant Ir (ppy)3(tris (2-phenylpyridinato) iridium), F2Irpic (bis [4, 6-difluorophenylpyridin-N, C2 'as blue phosphorescent dopant']Iridium (III) picolinate, iridium III bis [4, 6-di-fluorophenyl-pyridinyl-N, C2']picolinate), UDC corporation red phosphorescent dopant RD61, and the like. The doping concentration of the dopant is not particularly limited, but is preferably doped with the dopant in an amount of 0.01 to 15 parts by weight with respect to 100 parts by weight of the host. If the content of the dopant is less than 0.01 parts by weight, there is a problem that the coloring cannot be smoothly completed due to insufficient dopant amount, and if it exceeds 15 parts by weight, there is a problem that the efficiency is rapidly lowered due to concentration quenching phenomenon.
In the case where a phosphorescent dopant is used in combination in the light-emitting layer, it is preferable to further stack a hole-blocking material (HBL) by a vacuum evaporation method or a spin coating method in order to prevent a phenomenon that triplet excitons or holes diffuse into the electron-transporting layer. The hole-blocking substance that can be used in this case is not particularly limited, and any one selected from known materials used as a hole-blocking material can be used. For example, there may be mentioned
Examples of the oxadiazole derivative, the triazole derivative, the phenanthroline derivative, and the hole-blocking material described in jp 11-329734 a1 a include Balq (bis (8-hydroxy-2-methylquinoline) -diphenoylaluminum), and phenanthroline (phenanthroline) compounds (e.g., BCP (Bathocuproine, UDC)).
In this case, the electron transport layer is formed by a method such as vacuum deposition, spin coating, or casting, and is preferably formed by vacuum deposition.
The above-mentioned electron transport layer material plays a role of stably transporting electrons injected from the electron injection electrode,the kind thereof is not particularly limited, and for example, quinoline derivatives, particularly tris (8-hydroxyquinoline) aluminum (Alq), can be used3) Or ET4(6,6' - (3, 4-bis)
1, 1-dimethyl-1H-silole-2, 5-diyl) di-2, 2 '-bipyridine (6,6' - (3,4-
-1,1-
-1H-
-2,5-
)
-2,2'-
)). Further, an Electron Injection Layer (EIL) which is a substance having a function of easily injecting electrons from the cathode may be stacked on the electron transport layer, and LiF, NaCl, CsF, or Li may be used as the electron injection layer substance2O, BaO, etc.
The conditions for vapor deposition of the electron transport layer vary depending on the compound used, but are preferably selected within the range of conditions almost the same as those for formation of the hole injection layer.
In this case, the electron transport layer may be formed by a method such as vacuum deposition, spin coating, or casting, and is preferably formed by vacuum deposition.
Finally, the process is carried out in a batch,a metal for forming a cathode is formed on the electron injection layer by a method such as vacuum deposition or sputtering, and used as a cathode. Here, as the metal for forming the cathode, a metal having a low work function, an alloy, a conductive compound, and a mixture thereof can be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. In addition, in order to obtain a top-emitting element
A transmissive cathode using ITO or IZO may be used.
The organic light-emitting element of the present invention can realize not only an organic light-emitting element having an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode structure, but also structures of organic light-emitting elements having various structures, and one or two intermediate layers may be further formed as necessary.
As described above, the thickness of each organic layer formed according to the present invention may be adjusted according to the required degree, preferably 10 to 1000nm, more preferably 20 to 150 nm.
In addition, the organic layer including the compound represented by chemical formula 1 according to the present invention has advantages of uniform surface and excellent morphological stability since the thickness of the organic layer can be adjusted in a molecular unit.
The organic light-emitting device of the present invention includes the compound represented by chemical formula 1 having excellent charge transfer characteristics, high triplet energy, and high Tg, and thus can exhibit low driving voltage, high efficiency, low power consumption, and long lifetime.
Hereinafter, preferred examples are disclosed to facilitate understanding of the present invention, but the following examples merely illustrate the present invention, and the scope of the present invention is not limited to the following examples.
Synthesis of intermediate A
[ Synthesis of A-1 ]
In a round-bottomed flask, 41.17g of (1H-indol-3-yl) boronic acid and 50g of methyl 2-bromobenzoate were dissolved in 600ml of toluene, and 350ml of K was added2CO3(2M) and 8.1g of Pd (PPh)3)4Then, the mixture was stirred under reflux. The reaction was confirmed by TLC, and water was added, followed by termination of the reaction. The organic layer was extracted with EA, filtered under reduced pressure, and purified by column chromatography to obtain 42.1g of intermediate A-1 (yield 72%).
[ Synthesis of A-2 ]
42g of the above A-1 are dissolved in 1000ml of THF, and the temperature is then lowered to 0 ℃. 167ml of CH were slowly added3MgBr, and slowly raised to normal temperature and stirred for 1 hour, and then stirred under reflux. The organic layer was extracted with MC and filtered under reduced pressure, and then purified by column chromatography to obtain 28.6g of intermediate A-2 (yield 68%).
[ Synthesis of A ]
To 28g of A-2 described above, 280ml of acetic acid and 1.0ml of hydrochloric acid were added, followed by stirring under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column chromatography to obtain 15.3g of intermediate a (yield 60%).
Synthesis of intermediate B
[ Synthesis of B-1 ]
In a round-bottomed flask, 24.7g of (1H-indol-3-yl) boronic acid and 30g of methyl 2-bromobenzoate were dissolved in 350ml of toluene, and 210ml of K was added2CO3(2M) and 4.84g of Pd (PPh)3)4Then, the mixture was stirred under reflux. The reaction was confirmed by TLC, and water was added, followed by termination of the reaction. The organic layer was extracted with EA, filtered under reduced pressure, and purified by column chromatography to obtain 25.2g of intermediate B-1 (yield: 72%).
[ Synthesis of B-2 ]
42g of the above B-1 were dissolved in 600ml of THF, and the temperature was then lowered to 0 ℃.99 ml of PhMgBr was added slowly and slowly warmed to room temperature and stirred for 1 hour, followed by reflux stirring. The organic layer was extracted with MC and filtered under reduced pressure, followed by purification on a column to obtain 26.5g of intermediate B-2 (yield 71%).
[ Synthesis of B ]
To 26g of B-2 described above, 260ml of acetic acid and 1.0ml of hydrochloric acid were added, followed by stirring under reflux for 24 hours, and then the temperature was lowered to room temperature. The precipitated solid was filtered and purified by column chromatography to obtain 16.6g of intermediate B (yield 67%).
Example 1: synthesis of Compound 1
2.5g of the above intermediate A, 3.99g of 4-bromo-2, 6-diphenylpyridine, 1.54g of t-BuONa, 0.40g of Pd2(dba)30.5ml of (t-Bu)3P was dissolved in 40ml of toluene, followed by stirring under reflux. After confirming the completion of the reaction by TLC, the organic layer was extracted with MC and filtered under reduced pressure, followed by purification on a column to obtain 2.58g of compound 1 (yield 52%).
m/z：462.21(100.0％)、463.21(37.5％)、464.22(6.7％)
Example 2: synthesis of Compound 2
Compound 2 was synthesized in the same manner as Compound 1 except that 2-bromo-4, 6-diphenylpyridine was used in place of 4-bromo-2, 6-diphenylpyridine.
m/z：462.21(100.0％)、463.21(37.5％)、464.22(6.7％)
Example 3: synthesis of Compound 3
Compound 3 was synthesized in the same manner as Compound 1 except that 4-bromo-2, 6-diphenylpyrimidine was used in place of 4-bromo-2, 6-diphenylpyridine.
m/z：463.20(100.0％)、464.21(36.0％)、465.21(6.7％)、464.20(1.1％)
Example 4: synthesis of Compound 4
Compound 4 was synthesized by the same method as Compound 1 except that the reaction was carried out using 2-bromo-4, 6-diphenylpyrimidine instead of 4-bromo-2, 6-diphenylpyridine.
m/z：463.20(100.0％)、464.21(36.0％)、465.21(6.7％)、464.20(1.1％)
Example 5: synthesis of Compound 5
2.5g of the above intermediate A, 0.31g of NaH are introduced into 25ml of DMF and stirred. To this was slowly added dropwise a solution of 3.44g of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine dissolved in 35ml of DMF. After stirring at room temperature, completion of the reaction was confirmed by TLC, and after silica filtration and recrystallization, 2.44g of compound 5 was obtained (yield 49%).
m/z：464.20(100.0％)、465.20(36.1％)、466.21(5.9％)
Example 6: synthesis of Compound 6
Compound 6 was synthesized in the same manner as in Compound 1, except that the reaction was carried out using 4- (3-bromophenyl) -2, 6-diphenylpyrimidine instead of 4-bromo-2, 6-diphenylpyridine.
m/z：539.24(100.0％)、540.24(42.5％)、541.24(9.1％)、542.25(1.2％)、540.23(1.1％)
Example 7: synthesis of Compound 7
Compound 7 was synthesized by the same method as compound 1 except that 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine was used instead of 4-bromo-2, 6-diphenylpyridine.
m/z：540.23(100.0％)、541.23(42.6％)、542.24(8.4％)、543.24(1.2％)
Example 8: synthesis of Compound 8
Compound 8 was synthesized in the same manner as Compound 1, except that intermediate B was used in place of intermediate A and 2-bromo-4, 6-diphenylpyridine was used in place of 4-bromo-2, 6-diphenylpyridine.
m/z：587.24(100.0％)、588.24(46.8％)、589.24(11.1％)、590.25(1.6％)、588.23(1.1％)
Example 9: synthesis of Compound 9
Compound 9 was synthesized by the same method as compound 5 except that the reaction was carried out using intermediate B instead of intermediate a described above.
m/z：588.23(100.0％)、589.23(46.9％)、590.24(10.2％)、591.24(1.6％)
Example 10: synthesis of Compound 10
m/z：663.27(100.0％)、664.27(53.4％)、665.27(14.3％)、666.28(2.4％)、664.26(1.1％)
Example 11: synthesis of Compound 11
m/z：664.26(100.0％)、665.27(52.3％)、666.27(13.4％)、667.27(2.4％)、665.26(1.5％)
Example 12: synthesis of Compound 12
m/z：474.21(100.0％)、475.21(38.6％)、476.22(7.1％)
Example 13: synthesis of Compound 13
m/z：474.21(100.0％)、475.21(38.6％)、476.22(7.1％)
Manufacture of organic light-emitting element
An organic light-emitting element was manufactured according to the structure described in fig. 1. Regarding the organic light emitting element, anodes are laminated in this order from below
(hole-injecting electrode 11)/hole-injecting layer 12/hole-transporting layer 13/light-emitting layer 14/electron-transporting layer 15/cathode
(the electron injecting electrode 16).
The following materials were used for the hole injection layer 12, the hole transport layer 13, the light-emitting layer 14, and the electron transport layer 15 in examples and comparative examples.
Example 14
Will be provided with
The glass substrate coated with Indium Tin Oxide (ITO) in a thick film was cleaned with distilled water and ultrasonic waves. After the completion of the cleaning with distilled water, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, transferred to a plasma cleaner, cleaned with oxygen plasma for 5 minutes, and then subjected to a thermal vacuum coater (thermovacuator) to form a hole injection layer HT01 on the ITO substrate
NPB as hole transport layer
The film of (1). Then, as a light emitting layer, 10% of Ir (ppy) was doped in the compound 13Manufacture of
The film of (1). Then, as an electron transport layer, the electron transport layer was set to ET 01: liq (1: 1) manufacture
After the film of (2), LiF is produced
Film of (2), aluminum (Al)
Sealing (Encapsulation) the element in a glove box to produce a green organic light-emitting element.
Examples 15 to 26
In the same manner as in example 1, green organic light-emitting elements were produced in which the compounds 2 to 11 were used instead of the compound 1 as the light-emitting layer host.
Comparative example 1
A green organic light emitting element was produced by the same method except that CBP was used instead of compound 1 in the light emitting layer host in example 1.
Comparative example 2
A green organic light-emitting element was produced by the same method except that the comparative compound 1 was used instead of the compound 1 in the light-emitting layer host of example 1.
Evaluation of organic light-emitting element Performance
The organic light emitting elements of examples and comparative examples were evaluated for their performance by applying a voltage through a gieviy 2400 digital source meter (kinetey 2400source measurement unit), injecting electrons and holes, measuring the luminance at the time of light emission using a Konica Minolta (Konica Minolta) spectroradiometer (CS-2000), measuring the current density and luminance under atmospheric pressure conditions for the applied voltage, and showing the results in table 1.
TABLE 1
[ Table 1]
As shown in table 1, the physical properties of the organic light emitting devices in examples of the present invention were found to be superior to those in comparative examples 1 to 2 in all respects.
Industrial applicability
The light-emitting compound of the present invention has excellent charge transfer characteristics, high triplet energy, and high Tg, and therefore, when applied to an organic light-emitting element, the light-emitting compound can have a low driving voltage, high efficiency, low power consumption, and a long lifetime.
Claims (4)
1. A light-emitting compound represented by any one of the following structures:
in the above-described structure, the first and second electrodes,
each X is independently CR0，R0Is hydrogen; deuterium; or C1-30The alkyl group of (a) is,
R4and R5Each independently is hydrogen; deuterium; c1-30Alkyl groups of (a); or C6-50The aryl group of (a) is,
z is CR8Or N, R8Is hydrogen; deuterium; or C1-30The alkyl group of (a) is,
a is N-Ar1Wherein Ar is1Is C6-30The aryl group of (a) is,
ar is C6-38An arylene group of (a) to (b),
R6and R7Each independently is hydrogen; deuterium; c1-30Alkyl groups of (a); c6-30Aryl of (a); or C2-30The heteroaryl group of (a);
wherein the luminescent compound does not include N-phenyl-5, 6-dihydroindeno [2, 1-b ] indole.
2. A light-emitting compound characterized by being represented by any one of the following chemical formulae:
3. an organic light-emitting element comprising an anode, a cathode, and one or more organic layers containing the compound according to claim 1 or 2 between the two electrodes.
4. The organic light-emitting element according to claim 3, wherein the organic layer contains the compound according to claim 1 or 2 as a light-emitting host or a dopant.
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| KR10-2013-0141082 | 2013-11-20 | ||
| PCT/KR2014/011227 WO2015076601A1 (en) | 2013-11-20 | 2014-11-20 | Novel light emission compound and organic light emitting device comprising same |
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| KR20200099833A (en) | 2019-02-15 | 2020-08-25 | 삼성전자주식회사 | Condensed cyclic compound and organic light emitting device comprising the same |
| KR20200117249A (en) | 2019-04-03 | 2020-10-14 | 삼성전자주식회사 | Condensed cyclic compound and organic light emitting device comprising the same |
| KR102134380B1 (en) * | 2019-04-03 | 2020-07-16 | 주식회사 엘지화학 | Novel hetero-cyclic compound and organic light emitting device comprising the same |
| CN113831275B (en) * | 2021-09-01 | 2023-03-28 | 上海兆维科技发展有限公司 | Indole-substituted 6-phenylindenoindole derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049156A (en) * | 1989-06-22 | 1991-02-13 | 巴斯大学 | Indenoindole compounds |
| CN1231487C (en) * | 1997-11-12 | 2005-12-14 | 蒙特尔技术有限公司 | Metallocenes and catalysts for olefin-polymerisation |
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| JP5621187B2 (en) * | 2008-08-06 | 2014-11-05 | コニカミノルタ株式会社 | Organic electroluminescence element, display device, lighting device |
| KR20130096666A (en) * | 2012-02-22 | 2013-08-30 | 주식회사 엘지화학 | New compounds and organic electronic device using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049156A (en) * | 1989-06-22 | 1991-02-13 | 巴斯大学 | Indenoindole compounds |
| CN1231487C (en) * | 1997-11-12 | 2005-12-14 | 蒙特尔技术有限公司 | Metallocenes and catalysts for olefin-polymerisation |
Non-Patent Citations (1)
| Title |
|---|
| "Palladium-Catalyzed Synthesis of Benzosilolo[2,3-b]indoles via Cleavage of a C(sp3)-Si Bond and Consequent Intramolecular C(sp2)-Si Coupling";Y. Liang et al.，;《J. Am. Chem. Soc.》;20110425;第133卷(第24期);第9204-9207页 * |
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