CN106699573B - Spiro organic material and organic electroluminescent device using the same - Google Patents

Spiro organic material and organic electroluminescent device using the same Download PDF

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CN106699573B
CN106699573B CN201610458154.4A CN201610458154A CN106699573B CN 106699573 B CN106699573 B CN 106699573B CN 201610458154 A CN201610458154 A CN 201610458154A CN 106699573 B CN106699573 B CN 106699573B
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anthracene
fluorene
amine
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CN106699573A (en
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郑在皓
朴城珉
金俊佑
全永珉
南相镇
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Dae Joo Electronic Materials Co Ltd
Material Science Co Ltd
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Material Science Co Ltd
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Abstract

The present invention relates to an organic material containing spiro (benzo [ de ] anthracene-7.9' -fluorene) and an organic electroluminescent device using the same, and more particularly, to a novel spiro organic compound that can be used in an organic electroluminescent device and an organic electroluminescent device having excellent characteristics such as low power and high efficiency using the same.

Description

Spiro organic material and organic electroluminescent device using the same
Technical Field
The present invention relates to a novel spiro organic compound and an organic electroluminescent device using the same.
Background
Organic semiconductors are being developed for application to many electronic equipment of various types. Organic electroluminescent devices have been actively developed as light sources for flat panel displays such as wall-mounted Televisions (TVs) and displays, backlights of displays, illuminations, advertisement boards, etc., because they have a simple structure, have many advantages in a manufacturing process, have high luminance, excellent viewing angle characteristics, fast response speed, and low driving voltage, compared to other flat panel display devices such as conventional Liquid Crystal Displays (LCDs), Plasma Display Panels (PDPs), and Field Emission Displays (FEDs).
In an organic electroluminescent device, when a dc voltage is applied, holes injected from an anode and electrons injected from a cathode are recombined to form excitons as electron-hole pairs, and energy of the excitons is transferred to a light-emitting material to convert the excitons into light.
In order to improve the efficiency and stability of organic electroluminescent devices, studies on organic materials for organic electroluminescent devices of multilayer thin film structure type have been actively conducted since low voltage driving organic electroluminescent devices (c.w.tang, s.a. vanslyke, Applied physics letters, vol 51, page 913, 1987) in which a laminated organic thin film is formed between two opposite electrodes have been reported by dungeon cloud (c.w.tang) and the like of eastman kodak Company (eastman kodak Company).
In general, an organic electroluminescent device has a structure including a cathode (electron injection electrode), an anode (hole injection electrode), and one or more organic layers between the two electrodes. At this time, the organic electroluminescent device may include a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), or an Electron Injection Layer (EIL) as an organic layer in addition to the light emitting layer (EML) as an organic layer, and may further include an Electron Blocking Layer (EBL) or a Hole Blocking Layer (HBL) in light emitting characteristics of the light emitting layer. An organic electroluminescent device including all of these organic layers has a structure in which an anode/a hole injection layer/a hole transport layer/an electron blocking layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode are stacked in this order.
The materials used in organic electroluminescent devices are mostly pure organic materials or complexes of organic materials and metals, and may be classified into hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, and the like according to their applications. Here, an organic substance having a relatively small ionization energy is mainly used as the hole injecting substance or the hole transporting substance. On the other hand, an organic substance having a relatively large electronegativity is mainly used as the electron injecting substance or the electron transporting substance. The light-emitting layer contains two substances, a main substance and a dopant substance, the dopant substance is preferably a substance having high quantum efficiency, and the main substance is designed and used so as to cause energy transfer to the dopant substance well because the energy gap is larger than that of the dopant substance.
In addition to this, the substance used for the organic electroluminescent device preferably has the following properties.
First, it is preferable that the substance used for the organic electroluminescent device is a substance having excellent thermal stability. This is because joule heating (joule heating) occurs in the organic electroluminescent device due to the movement of a plurality of charges. Currently, N '-diphenyl-N, N' -di (3-tolyl) -1,1 '-biphenyl-4, 4' -diamine (TPD) or N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), which is mainly used as a hole transport layer material, is also low in glass transition temperature (Tg) of 60 ℃ and 96 ℃, respectively, and therefore, when driving is performed in a high temperature environment, crystallization is caused and a phenomenon of reducing light emission efficiency occurs.
Secondly, in order to obtain a highly efficient organic electroluminescent device capable of low voltage driving, it is necessary to smoothly transfer holes or electrons injected into the organic electroluminescent device to the light emitting layer and to prevent the injected holes and electrons from escaping to the outside of the light emitting layer. For this reason, a substance used for an organic electroluminescent device should have an appropriate band gap (band gap) and Highest Occupied Molecular (HOMO) or Lowest Unoccupied Molecular (LUMO) energy level.
In addition, the materials used in organic electroluminescent devices should have excellent chemical stability, charge mobility, and surface characteristics with respect to electrodes or adjacent layers. Further, by providing appropriate hole or electron mobility, the density of holes and electrons in the light-emitting layer of the organic electroluminescent device can be equalized, and the formation of excitons can be maximized.
In order to make the organic electroluminescent device sufficiently exhibit the above excellent characteristics, a substance for forming an organic layer in the device, for example, a hole injecting substance, a hole transporting substance, a light emitting substance, an electron transporting substance, an electron injecting substance, and the like should be a stable and effective material, but development of a stable and effective organic material for an organic electroluminescent device has not been sufficiently achieved so far. Therefore, in the field of the present invention, there is still a need to develop a new material having low voltage driving, high efficiency and long life.
Disclosure of Invention
An object of the present invention is to provide a novel spiro organic compound which can be suitably used as an electron blocking substance or a hole transporting substance for providing a low-power, high-efficiency organic electroluminescent device.
A first embodiment of the present invention provides a compound represented by the following chemical formula 1.
Chemical formula 1:
Figure BDA0001026240440000031
in the chemical formula 1 described above,
R1to R18Each independently selected from 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, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a halogen group, a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 2 to 30 carbon atoms, a substituted or, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and a functional group represented by the following chemical formula 2,
only, R1To R18Is a functional group represented by the following chemical formula 2,
chemical formula 2:
Figure BDA0001026240440000032
in the above-described chemical formula 2,
l is selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 18 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 18 carbon atoms, or
L and R of the adjacent spirocyclic nucleus1To R18Is linked to form a saturated or unsaturated ring, or is linked to an adjacent nitrogen (N) atom, Ar1Or Ar2Are linked to form a heterocyclic group having 5 to 18 nuclear atoms,
Ar1and Ar2Each 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, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, 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,
Ar1and Ar2Each independently bonded to adjacent nitrogen (N) atoms and L to form saturated or unsaturated rings having 5 to 18 nuclear atoms, or bonded to adjacent nitrogen (N) atoms to form saturated or unsaturated rings having 5 to 18 nuclear atoms, or Ar is a single bond in the case where L is a bond1And Ar2Each independently linked to the nitrogen (N) atom and the spiro nucleus to form a saturated or unsaturated ring,
r is as defined above1To R18、L、Ar1And Ar2The substituents of (a) may be the same or different substituents and are each independently selected from the group consisting of hydrogen, deuterium, cyano, nitro, halo, hydroxyl, a substituted or unsubstituted alkyl group having 1 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, a cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, 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 aralkyl group having 6 to 24 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atomsOr one or more substituents selected from the group consisting of an unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamine group having 2 to 24 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.
In the present invention, R1To R18And Ar1To Ar2Each independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl alcohol, tert-butyl, cyclohexyl, trimethylsilyl, triphenylsilyl, substituted or unsubstituted phenyl, biphenyl, terphenyl, biphenylyl, triphenylenyl, naphthyl, phenanthrenyl, fluorenyl, pyrenyl, dibenzofuranyl, benzofuranyl, phenylsulfinyl, dibenzothiophene, carbazolyl, spirospirospirospirobifluorenyl, anthracenyl, acenaphthenyl, pyridyl, carbolinyl, quinolyl, isoquinolyl, thianthrenyl, 9H-thianthrenyl, xanthenyl, phenoxaxanthenyl, 9 dimethyl-9, 10-dihydroanthracene, tetrahydronaphthyl, tetramethylindolyl and 4a, 9 a-dimethylhexahydrocarbazolyl,
l may be selected from the group consisting of a single bond, phenyl, biphenyl, terphenyl, naphthyl, carbazole, dibenzofuran, and dibenzothiophene.
A second embodiment of the present invention provides an organic electroluminescent device comprising: a first electrode; a second electrode; and at least one organic film provided between the first electrode and the second electrode, wherein the organic film contains the compound according to the first embodiment.
Preferably, the organic film may be a light-emitting layer, a hole injection layer, a hole transport layer, or an electron blocking layer.
The present invention will be described in detail below.
According to the present invention, a compound whose molecule is designed using spiro (benzo [ de ] anthracene-7.9' -fluorene) as a core can be introduced between the hole transporting layer and the light-emitting layer.
When the ratio of holes to electrons flowing into the light-emitting layer is 1:1, the light-emitting efficiency can be maximized. When holes do not combine with electrons, the holes move to the cathode (cathode) side, and the electrons move to the anode (anode) side. This phenomenon occurs in the case where the energy barrier between the light-emitting layer and the electron injection layer is small from the viewpoint of holes, and occurs in the case where the energy barrier between the light-emitting layer and the hole movement layer is small from the viewpoint of electrons, and this problem can be solved by adjusting the energy barrier between the light-emitting layer and the adjacent layer. Another reason for causing the ratio of holes and electrons to be inconstant in the light emitting layer is various voltage distributions within the organic electroluminescent device. Initially, all voltages are applied between the two electrodes before the application of the electric charges, but as the applied voltage increases, the electric charges are injected, and holes are accumulated between the hole moving layer and the light emitting layer, and electrons are accumulated between the electron moving layer and the light emitting layer. The plurality of charges accumulated in this manner forms an electric attraction force to the opposite charges, so that the holes function to increase the mobility of the electrons, and the electrons function to increase the mobility of the holes. When holes are accumulated too much, the electron density in the light-emitting layer is increased, and when holes are accumulated less, the hole density in the light-emitting layer is increased. In the case where the density of electrons is increased in the light-emitting Layer, as an example of a solution, a substance having appropriate resistance and energy level (hereinafter, referred to as an "Electron Blocking Layer-EBL") is introduced between the light-emitting Layer and the hole transport Layer to have charge balance. In the case where the triplet energy of the electron blocking layer is designed to be larger than the triplet energy of the light emitting layer, there is an effect of collecting triplet excitons in the light emitting layer, and therefore, the singlet formation ratio can be increased by the interaction between triplet excitons in the light emitting layer, and the light emitting efficiency can be improved. In the case where the density of holes is high, a method opposite to the above method can be devised, so that the light emitting efficiency can be improved.
The compound of the present invention can be used in a hole transport layer or an electron blocking layer, but can be used in a light-emitting layer, an electron transport layer, and a cover layer by various molecular designs.
The compound of the present invention has an advantage that a spiro (benzo [ de ] anthracene-7.9' -fluorene) structure can be applied to a core to increase a band gap, and particularly, has an advantage that a glass transition temperature can be greatly increased compared to other spiro structures due to a large molecular weight of the spiro core. Therefore, the energy level of the highest occupied molecule can be changed in various ways by introducing a disubstituted amine into the parent nucleus and changing the amine substituent in various ways. Thus, Indium Tin Oxide (ITO) and a hole injection barrier of the hole transport layer can be variously changed, and an appropriate energy level can be provided between the hole transport layer and the light emitting layer, whereby adjustment can be made to improve exciton generation efficiency in the light emitting layer.
Thus, in one embodiment of the present invention, a compound having a spiro parent core structure that is suitable for a hole transport and electron blocking layer material is prepared.
The compound represented by chemical formula 1 of the present invention may be used for the preparation of an Organic Light Emitting Diode (OLED) using a solution process other than the evaporation method, and in chemical formula 1, R may be used if appropriately selected1To R18、Ar1And Ar2The compound represented by the above chemical formula 1 may have increased solubility and improved film processing (film processing) properties. For example, the length of the aliphatic (aliphatic) substituent can be adjusted to improve solubility, and thus the method can be applied to a wet epitaxial process such as inkjet or spin coating. When a functional group that is cured by Ultraviolet (UV) or heat is introduced to the end of the spiro nucleus or the functional group, the polymer is formed by ultraviolet curing or heat curing after the coating is performed through a solution process. Thus, even if the solution process is applied to the upper layer, the solvent can be prevented from being washed away.
Representative examples of the compound represented by the above chemical formula 1 are as follows.
Figure BDA0001026240440000071
Figure BDA0001026240440000081
Figure BDA0001026240440000091
Figure BDA0001026240440000101
Figure BDA0001026240440000111
Figure BDA0001026240440000121
Figure BDA0001026240440000131
Figure BDA0001026240440000141
Figure BDA0001026240440000151
Figure BDA0001026240440000161
Figure BDA0001026240440000171
Figure BDA0001026240440000181
Figure BDA0001026240440000191
Figure BDA0001026240440000201
Figure BDA0001026240440000211
Figure BDA0001026240440000221
Figure BDA0001026240440000231
Figure BDA0001026240440000241
Figure BDA0001026240440000251
Figure BDA0001026240440000261
Figure BDA0001026240440000271
Figure BDA0001026240440000281
Figure BDA0001026240440000291
Figure BDA0001026240440000301
Figure BDA0001026240440000311
Figure BDA0001026240440000321
Figure BDA0001026240440000331
Figure BDA0001026240440000341
Further, as an example of the present invention, the compound represented by the above chemical formula 1 can be prepared as the following reaction formula 1 or reaction formula 2, but the preparation method of the compound represented by the above chemical formula 1 is not limited thereto, and various preparation methods can be applied.
Reaction formula 1:
Figure BDA0001026240440000342
reaction formula 2:
Figure BDA0001026240440000343
in the above reaction formulae 1 and 2, R is1To R18、L、Ar1And Ar2Is as defined above, R1' to R18' 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, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a halogen group, a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group, a substituted orA heteroaryl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a boronic acid group, a substituted or unsubstituted boronic acid ester group and
Figure BDA0001026240440000351
in the group consisting of.
Specifically, in the case of the above reaction formula 1, at R1' to R18In the case where at least one of these is a halogen group, A in the above reaction formula 1 is a boronic acid group or a boronic ester group, and in R1' to R18When at least one of' is a boronic acid group or a boronic ester group, a in the above reaction formula 1 is a halogen group, and thus can be represented by the following reaction formulae 3 and 4, respectively.
Reaction formula 3:
Figure BDA0001026240440000352
reaction formula 4:
Figure BDA0001026240440000353
in the above reaction formula 2, in R1' to R18One of the' is
Figure BDA0001026240440000354
When A is a halogen group (e.g., Br), it can be represented by the following reaction formula 5, wherein R is1' to R18One of the' is
Figure BDA0001026240440000355
When a is a halogen group (e.g., Br) and L is a single bond, it can be represented by the following reaction formula 6.
Reaction formula 5:
Figure BDA0001026240440000356
reaction formula 6:
Figure BDA0001026240440000361
in the above reaction formulae 1 and 2, the halogen group is preferably chlorine, bromine or iodine.
The present invention provides a method for preparing a compound represented by the following chemical formula 1, the method for preparing a compound represented by the following chemical formula 1 including the step 1 of reacting a compound represented by the following chemical formula 3 with a compound represented by the following chemical formula 4 in the step 1.
Chemical formula 1:
Figure BDA0001026240440000362
chemical formula 3:
Figure BDA0001026240440000363
chemical formula 4:
Figure BDA0001026240440000364
in the above chemical formula, R1To R18、L、A、Ar1And Ar2、R1' to R18' is as defined above.
The above step 1 is a step of preparing the compound represented by chemical formula 1 by reacting the compound of spiro skeleton represented by chemical formula 3 and the amine compound represented by chemical formula 4.
In the present invention, toluene may be used as the reaction solvent of the above step 1), and is not limited thereto.
In the present invention, the reaction temperature of the above step 1) may be in the range of 70 to 100 ℃, and is not limited thereto. If the reaction temperature is less than 70 ℃, there is a disadvantage of a prolonged reaction time due to a slow reaction rate, and if the reaction temperature is more than 100 ℃, impurities are generated, thereby having a disadvantage of a decreased yield.
In the present invention, the reaction time of the above step 1) may be in the range of 12 to 24 hours, and is not limited thereto. If the reaction time is less than 12 hours, the reaction is not completed and the starting material remains, and in general, the reaction time is completed within 24 hours, so that a reaction time of more than 24 hours is not necessary.
In the present invention, preferably, the step 1) may be carried out in tris (dibenzylideneacetone) palladium (Pd)2(dba)3) Tri-tert-butylphosphine (t-Bu)3P) and sodium tert-butoxide (t-BuONa), but not limited thereto.
The present invention provides an organic electroluminescent device comprising a compound represented by chemical formula 1, preferably, one compound selected from the group consisting of compound 1 to compound 493. In this case, the organic electroluminescent device may include a hole injection layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
The organic electroluminescent device of the present invention includes a first electrode, a second electrode, and at least one organic film between the first electrode and the second electrode, and the organic film includes a compound represented by chemical formula 1, preferably, one of compounds 1 to 493. Preferably, the organic film may be a light emitting layer, a hole injection layer, a hole transport layer, or an electron blocking layer, and may further include one or more layers 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 between the first electrode and the second electrode. As an example, the organic electroluminescent device of the present invention includes an anode, a cathode, at least one light emitting layer between the two electrodes, and an organic layer having a multi-layer structure including an electron blocking layer and/or a hole transporting layer, the electron blocking layer and/or the hole transporting layer including a compound represented by chemical formula 1, preferably, one or more compounds among compounds 1 to 493. For example, a multilayer organic electroluminescent device has a multilayer structure in which a substrate, an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode are stacked from bottom to top.
The substrate, the anode, the hole injection layer, the light emitting layer, the hole blocking layer, the electron transport layer, the electron injection layer, and the cathode of the organic electroluminescent device of the present invention are composed of materials generally used in organic electroluminescent devices, and one of the electron blocking layer and/or the hole transport layer may include a compound represented by chemical formula 1, and preferably, may include one or more compounds of compounds 1 to 493. The electron blocking layer and/or the hole transporting layer may further include a general electron blocking substance and/or a hole transporting substance in addition to the compound represented by chemical formula 1.
In particular, in the case of an electron blocking layer and/or a hole transporting layer, the compound represented by chemical formula 1 of the present invention may be used, and preferably, two or more of the compounds 1 to 493 may be used alone or in combination. In the case of using the compound represented by chemical formula 1, preferably, using one or more of the compounds 1 to 493 as the electron blocking substance and/or the hole transporting substance, an amount of 0.01 to 100 weight percent, for example, 0.01 to 20 weight percent, 20 to 80 weight percent, 80 to 100 weight percent, or the like, may be added with respect to the total weight of the electron blocking layer and/or the hole transporting layer.
In the present invention, an organic substance capable of hole injection can easily inject holes from the anode, and preferably has characteristics such as an appropriate ionization energy (ionizationpotential) for hole injection from the anode, a high surface adhesion to the anode, and non-absorbability in the visible light range, and examples of the substituent capable of hole injection include, but are not limited to, metalloporphyrin, oligothiophene, an organic substance of arylamine series, an organic substance of hexacyano-hexaazatriphenylene, quinacridone (quinacridone) series, an organic substance of perylene (perylene) series, and anthraquinone.
In the present invention, a known light-emitting main substance or dopant substance used as a light-emitting main (host) substance or a dopant (dopant) substance can be used for the light-emitting layer. As the light-emitting substance, a substance having excellent quantum efficiency for fluorescence or phosphorescence is preferably used as a substance which can receive holes and electrons from the hole-transporting layer and the electron-transporting layer, respectively, and can emit light in a visible light range by performing combination. Specific examples of the light-emitting substance, the main substance, or the dopant substance include anthracene, naphthalene, phenanthrene, pyrene, tetraphenyl, coronene, chrysene, fluorescein, perylene, phthalocyanine perylene, perinone, diphenoxyphthalide, naphthaline diphenoxyphthalide, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, azinane, bisbenzoxazole, stilbene, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, stilbene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, cyanine, imidazole chelate oxygen compound, quinacridone, rubrene, carbazole series compound, benzothiazole and benzimidazole series compound, spiro (spiro) compound, polyfluorene, fluorescent pigment, and a mixture thereof, but are not limited thereto. In the case of selecting a dopant substance, a substance having both fluorescence or phosphorescence with high efficiency and having a band gap (bandgap) equal to or smaller than that of the main substance should be preferable.
In particular, in the organic electroluminescent device of the present invention, the above-mentioned light-emitting layer may contain a fluorescent or phosphorescent substance.
An organic substance capable of electron transfer is a compound having an electron-withdrawing substance, and examples of the substituent capable of electron transfer include, but are not limited to, compounds having a functional group capable of withdrawing electrons by resonance, such as a cyano group, oxadiazole, or triazole.
The layers constituting the organic electroluminescent device, that is, the organic film, may be formed by a vacuum evaporation method or a solution process. Specifically, the organic film can be formed by applying any method having good smoothness to a dry epitaxial method such as vacuum deposition, sputtering, plasma, or ion plating, or a wet epitaxial method such as radiation coating, immersion coating, or flow coating. The thickness of the film is not particularly limited, but if the thickness of the film is too thick, a high applied voltage is required to obtain a predetermined light output, resulting in deterioration of efficiency, whereas if the thickness of the film is too thin, a sufficient light emission luminance cannot be obtained even if an electric field is applied due to generation of a pin hole (pin hole) or the like. Generally, the thickness of the film is preferably in the range of 5nm to 10 μm, but more preferably in the range of 50nm to 400 nm.
According to the present invention, a compound having a spiro ring (benzo [ de ] anthracene-7.9' -fluorene) as a molecular design can be used not only as a hole transport layer and/or an electron blocking layer, but also as a light emitting layer, an electron transport layer, and a cover layer by various molecular designs.
The compound of the invention can be applied to a spiro structure in a mother nucleus to increase band gap, and particularly, compared with other spiro structures, the compound can greatly improve glass transition temperature due to the large molecular weight of the spiro mother nucleus. Further, by introducing a disubstituted amine into the parent nucleus and changing the amine substituent in various ways, the energy level of the highest occupied molecule can be changed in various ways. Thus, indium tin oxide and a hole injection barrier of the hole transport layer can be variously changed, and an appropriate energy level can be provided between the hole transport layer and the light emitting layer, whereby adjustment can be made to improve exciton generation efficiency in the light emitting layer.
Detailed Description
The present invention will be described in more detail below with reference to examples. These examples are merely for more specifically illustrating the present invention, and the scope of the present invention is not limited to these examples.
Example 1: preparation of Compound 1
Figure BDA0001026240440000401
3.21g (10mmol) of bis ([1, 1' -biphenyl) were dissolved in 30ml of toluene]-4-yl) amine and 4.45g (10mmol) of 2' -bromospiro [ benzo [ de ]]Anthracene-7, 9' -fluorene]Then, 2.88g (30mmol) of sodium tert-butoxide, 161mg (0.4mmol) of tri-tert-butylphosphine (50 wt% in toluene), and 115mg (0.2mmol) of bis (dibenzylideneacetone) palladium (0) were added, followed by stirring and refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled at ordinary temperature, and 50ml of ethyl acetate and 50ml of H were added2O to extract the organic layer. Using MgSO4The organic layer was treated, filtered, dried, and subjected to column formation using n-hexane/dimethylammonium chloride, thereby obtaining compound 1 with a yield of 85% (5.83 g).
Example 2: preparation of Compound 2
Compound 2 was prepared in the same manner as in example 1, except that 4.58g (10mmol) of N-phenylspiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] -2 ' -amine and 2.13g (10mmol) of 1-bromo-4- (tert-butyl) benzene were used in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 3: preparation of Compound 6
Compound 6 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N- ([1, 1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 2' -bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 4: preparation of Compound 9
Compound 9 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 5: preparation of Compound 10
Compound 10 was prepared in the same manner as in example 1, except for using 3.75g (10mmol) of N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ de ] anthracene-7, 9 ' -fluorene ].
Example 6: preparation of Compound 13
Compound 13 was prepared in the same manner as in example 1 except for using 4.58g (10mmol) of N-phenylspiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] -2 ' -amine and 1.75g (10mmol) of 1-bromo-4-fluorobenzene in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 7: preparation of Compound 15
Compound 15 was prepared in the same manner as in example 1, except for using 4.58g (10mmol) of N-phenylspiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] -2 ' -amine and 2.63g (10mmol) of 4-bromodibenzo [ b, d ] thiophene in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 8: preparation of Compound 19
Compound 19 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-3-amine and 4.45g (10mmol) of 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 9: preparation of Compound 20
Compound 20 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N- ([1, 1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-3-amine and 4.45g (10mmol) of 2' -bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 10: preparation of Compound 29
Compound 29 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N, 6-diphenyldibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 11: preparation of Compound 30
Compound 30 was prepared in the same manner as in example 1, except for using 4.58g (10mmol) of N-phenylspiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] -2 ' -amine and 3.22g (10mmol) of 3-bromo-9-phenyl-9H-carbazole instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 12: preparation of Compound 37
Compound 37 was prepared in the same manner as in example 1, except for using 2.85g (10mmol) of 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine and 4.45g (10mmol) of 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 13: preparation of Compound 38
Compound 38 was prepared in the same manner as in example 1, except for using 3.61g (10mmol) of N- ([1, 1 '-biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine and 4.45g (10mmol) of 2' -bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ de ] anthracene-7, 9' -fluorene ].
Example 14: preparation of Compound 47
Compound 47 was prepared in the same manner as in example 1, except for using 3.61g (10mmol) of N- ([1, 1 '-biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine and 4.45g (10mmol) of 2' -bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ de ] anthracene-7, 9' -fluorene ].
Example 15: preparation of Compound 63
Compound 63 was prepared in the same manner as in example 1 except for using 3.35g (10mmol) of N- ([1, 1 '-biphenyl ] -2-yl) dibenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 2' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ de ] anthracene-7, 9' -fluorene ].
Example 16: preparation of Compound 64
Compound 64 was prepared in the same manner as in example 1, except for using 4.58g (10mmol) of N-phenylspiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] -2 ' -amine and 2.07g (10mmol) of 1-bromonaphthalene in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 17: preparation of Compound 65
Compound 65 was prepared in the same manner as in example 1, except for using 4.58g (10mmol) of N-phenylspiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] -2 ' -amine and 2.29g (10mmol) of (4-bromophenyl) trimethylsilane in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 18: preparation of Compound 74
Compound 74 was prepared in the same manner as in example 1 except for using 2.59g (10mmol) of N-phenyldibenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 2 ' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 19: preparation of Compound 84
Compound 84 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-3-amine and 4.77g (10mmol) of 2 ' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 20: preparation of Compound 94
Compound 94 was prepared in the same manner as in example 1 except for using 3.35g (10mmol) of N, 6-diphenyldibenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 2 ' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 21: preparation of Compound 103
Compound 103 was prepared in the same manner as in example 1, except for using 3.61g (10mmol) of N- ([1, 1 '-biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine and 4.77g (10mmol) of 2' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 22: preparation of Compound 125
Compound 125 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N- ([1, 1 '-biphenyl ] -2-yl) dibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 2' -bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 23: preparation of Compound 128
Compound 128 was prepared in the same manner as in example 1 except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-4-amine and 5.98g (10mmol) of 2 ' - (4 ' -bromo- [1, 1 ' -biphenyl ] -4-yl) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ de ] anthracene-7, 9 ' -fluorene ].
Example 24: preparation of Compound 139
Compound 139 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N- ([1, 1 ' -biphenyl ] -4-yl) dibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 25: preparation of Compound 142
Compound 142 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 26: preparation of Compound 143
Compound 143 was prepared in the same manner as in example 1, except for using 3.75g (10mmol) of N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ de ] anthracene-7, 9' -fluorene ].
Example 27: preparation of Compound 152
Compound 152 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-3-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 28: preparation of Compound 153
Compound 153 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N- ([1, 1 ' -biphenyl ] -4-yl) dibenzo [ b, d ] furan-3-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 29: preparation of Compound 162
Compound 162 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N, 6-diphenyldibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 30: preparation of Compound 170
Compound 170 was prepared in the same manner as in example 1, except for using 2.85g (10mmol) of 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 31: preparation of Compound 171
Compound 171 was prepared in the same manner as in example 1, except for using 3.61g (10mmol) of N- ([1, 1 ' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine and 4.45g (10mmol) of 9-bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ de ] anthracene-7, 9 ' -fluorene ].
Example 32: preparation of Compound 180
Compound 180 was prepared in the same manner as in example 1, except for using 3.61g (10mmol) of N- ([1, 1 ' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine and 4.45g (10mmol) of 9-chlorospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 33: preparation of Compound 189
Compound 189 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N- ([1, 1 ' -biphenyl ] -2-yl) dibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 9-chlorospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 34: preparation of compound 198
Compound 198 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 9- (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 35: preparation of Compound 208
Compound 208 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-3-amine and 4.77g (10mmol) of 9- (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 36: preparation of Compound 226
Compound 226 was prepared in the same manner as in example 1, except for using 2.85g (10mmol) of 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine and 4.77g (10mmol) of 9- (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 37: preparation of Compound 318
Compound 318 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 3- (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 38: preparation of Compound 328
Compound 328 was prepared in the same manner as in example 1, except for using 2.59g (10mmol) of N-phenyldibenzo [ b, d ] furan-3-amine and 4.77g (10mmol) of 3- (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 39: preparation of Compound 346
Compound 346 was prepared in the same manner as in example 1, except for using 2.85g (10mmol) of 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine and 4.77g (10mmol) of 3- (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 40: preparation of Compound 379
Compound 379 was prepared in the same manner as in example 1 except for using 3.35g (10mmol) of N- ([1, 1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 4' -chromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 41: preparation of Compound 382
Compound 382 was prepared in the same manner as in example 1 except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 4 ' -chromyspirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 42: preparation of compound 383
Compound 383 was prepared in the same manner as in example 1, except for using 3.75g (10mmol) of N- (9, 9-dimethyl-9H-fluoren-2-yl) dibenzo [ b, d ] furan-4-amine e and 4.45g (10mmol) of 4 ' -chromyspiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ de ] anthracene-7, 9 ' -fluorene ].
Example 43: preparation of Compound 392
Compound 392 was prepared in the same manner as in example 1, except that 2.59g (10mmol) of N-phenyldibenzo [ b, d ] furan-3-amine and 4.45g (10mmol) of 4 ' -chromyspirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ] were used in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 44: preparation of compound 393
Compound 393 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N- ([1, 1 '-biphenyl ] -4-yl) dibenzo [ b, d ] furan-3-amine and 4.45g (10mmol) of 4' -chromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] instead of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ benzo [ de ] anthracene-7, 9' -fluorene ].
Example 45: preparation of Compound 402
Compound 402 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N, 6-diphenyldibenzo [ b, d ] furan-4-amine and 4.45g (10mmol) of 4 ' -chromyspirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 46: preparation of Compound 410
Compound 410 was prepared in the same manner as in example 1, except for using 2.85g (10mmol) of 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine and 4.45g (10mmol) of 4 ' -chromyspirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ] in place of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospirocyclo [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 47: preparation of Compound 411
Compound 411 was prepared in the same manner as in example 1, except for using 3.61g (10mmol) of N- ([1, 1 '-biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine and 4.45g (10mmol) of 4' -chromyspiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ de ] anthracene-7, 9' -fluorene ].
Example 48: preparation of Compound 420
Compound 420 was prepared in the same manner as in example 1, except for using 3.61g (10mmol) of N- ([1, 1 '-biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine and 4.45g (10mmol) of 4' -bromospiro [ benzo [ de ] anthracene-7, 9 '-fluorene ] in place of bis ([1, 1' -biphenyl ] -4-yl) amine and 2 '-bromospiro [ de ] anthracene-7, 9' -fluorene ].
Example 49: preparation of Compound 438
Compound 438 was prepared in the same manner as in example 1 except for using 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 4 ' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 50: preparation of Compound 448
Compound 448 was prepared in the same manner as in example 1, except that 2.59g (10mmol) of N-phenylbenzo [ b, d ] furan-3-amine and 4.77g (10mmol) of 4 ' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] were used instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 51: preparation of Compound 458
Compound 458 was prepared in the same manner as in example 1, except for using 3.35g (10mmol) of N, 6-diphenyldibenzo [ b, d ] furan-4-amine and 4.77g (10mmol) of 4 ' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
Example 52: preparation of Compound 466
Compound 466 was prepared in the same manner as in example 1 except for using 2.85g (10mmol) of 9, 9-dimethyl-N-phenyl-9H-fluoren-2-amine and 4.77g (10mmol) of 4 ' - (4-chlorobenzene) spiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ] instead of bis ([1, 1 ' -biphenyl ] -4-yl) amine and 2 ' -bromospiro [ benzo [ de ] anthracene-7, 9 ' -fluorene ].
nmR and yield data for the various compounds synthesized above are shown in tables 1 through 4 below.
TABLE 1
Figure BDA0001026240440000481
TABLE 2
Figure BDA0001026240440000491
TABLE 3
Figure BDA0001026240440000501
TABLE 4
Figure BDA0001026240440000511
Experimental example 1: preparation of organic electroluminescent devices Using example Compounds and analysis of the Properties of these devices
As shown in table 5 below, organic electroluminescent devices were prepared using the example compounds as electron blocking layers according to the following procedures.
First, an anode was formed using indium tin oxide on a substrate on which a reflective layer was formed, and N was used2The plasma performs a surface treatment. Evaporating N4, N4, N4 ', N4 ' -tetra ([1, 1 ' -biphenyl) on the surface]-4-yl) - [1, 1' -biphenyl]-4, 4' -diamine as Hole Injection Layer (HIL) and doped with about 3% P-doping as dopant species, thereby forming a thickness of 100 a. Next, N4, N4, N4 ', N4 ' -tetrakis ([1, 1 ' -biphenyl) was vacuum-deposited on the hole injection layer]-4-yl) - [1, 1' -biphenyl]The compound of each example was formed as an electron blocking layer with a thickness of 150 a on top of each hole transporting layer, αβ -ADN, which was capable of forming a blue light emitting layer, was deposited as a light emitting layer (EML) on top of the electron blocking layer, and about 5% of N1, N1, N6, N6-tetrakis (4) was doped- (1-silyl) phenyl) pyrene-1, 6-diamine as a dopant to form a light emitting layer of 200 a thickness.
2- (4- (9, 10-bis (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ] is mixed above it in a weight ratio of 1:1]Imidazole and 8-hydroxyquinoline Lithium (LiQ), and an electron transport layer was deposited at a thickness of 360 a, and magnesium (Mg) and silver (Ag) at a ratio of 9:1 at a thickness of 160 a were deposited as a cathode, thereby forming a cathode. 650 thickness of N4, N4 ' -diphenyl-N4, N4 ' -bis (4- (9-phenyl-9H-carbazol-3-yl) phenyl) - [1, 1 ' -biphenyl was evaporated on the cathode]-4, 4' -diamine as a capping layer (CPL). Sealing cover (seal cap) containing 39-30 moisture absorbent can be bonded on the covering layer as ultraviolet curing type adhesive for O in air2Or moisture, thereby producing an organic electroluminescent device.
As comparative examples, organic electroluminescent devices were produced in the same manner as described above except that N, N '-Bis- (1-naphthalene) N, N' -diphenyl- (1,1 '-biphenyl) -4, 4' -diamine (NPD; N, N '-Bis- (1-naphthyl) -N, N' -Bis-phenyl- (1,1 '-biphenyl) -4, 4' -diamine) was used as an electron-blocking layer in place of the example compounds.
At 10mA/cm2The organic electroluminescent device prepared as described above was subjected to device performance analysis under the conditions of (1), and the results thereof are shown in the following table 5.
TABLE 5
Figure BDA0001026240440000521
Figure BDA0001026240440000531
As shown in the evaluation of the device shown in table 5, when the compound of the present invention is applied as an electron blocking layer to an organic electroluminescent device, the voltage exhibits a characteristic of being lower by about 0.9 to 1.2V under the same current density condition and the characteristic of increasing the external quantum efficiency to 27% at the maximum, although the current efficiency and the CIEy value are similar to those of the comparative example. Therefore, it is found that when the compound of the present invention is used as an electron blocking layer in an organic electroluminescent device, high power efficiency and high current efficiency can be achieved.

Claims (3)

1. An organic electroluminescent device having a light-emitting layer,
the method comprises the following steps: a first electrode;
a second electrode; and
at least one organic film disposed between the first electrode and the second electrode,
the above-mentioned organic electroluminescent device is characterized in that,
the organic film includes one or more layers 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 organic film includes an electron blocking layer containing a compound represented by the following chemical formula 1;
chemical formula 1:
Figure FDA0002506553440000011
in the above-described chemical formula 1,
R1to R18Is R2、R7、R12And R14One is a functional group represented by the following chemical formula 2, R which is not a functional group represented by chemical formula 21To R18Is a hydrogen atom, and is,
chemical formula 2:
Figure FDA0002506553440000012
in the above-described chemical formula 2,
l is selected from the group consisting of a single bond, phenyl, biphenyl, naphthyl,
Ar1selected from biphenyl and dibenzofuranyl; and Ar2Selected from phenyl and biphenylA phenyl group, a terphenyl group, a dibenzofuranyl group, a dibenzothiophene group, a benzsulfinyl group, and a carbazolyl group,
l, Ar as described above1And Ar2Optionally substituted with at least one substituent selected from: hydrogen, deuterium, a cyano group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a heterocycloalkyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms,
provided that the compound represented by chemical formula 1 is not the following compound 114:
Figure FDA0002506553440000021
2. an organic electroluminescent device having a light-emitting layer,
the method comprises the following steps: a first electrode;
a second electrode; and
at least one organic film disposed between the first electrode and the second electrode,
the above-mentioned organic electroluminescent device is characterized in that,
the organic film includes one or more layers 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 organic film includes an electron blocking layer containing a compound represented by any one of the following structures:
Figure FDA0002506553440000031
Figure FDA0002506553440000041
Figure FDA0002506553440000051
Figure FDA0002506553440000061
Figure FDA0002506553440000071
Figure FDA0002506553440000081
Figure FDA0002506553440000091
Figure FDA0002506553440000101
Figure FDA0002506553440000111
Figure FDA0002506553440000121
Figure FDA0002506553440000131
Figure FDA0002506553440000141
Figure FDA0002506553440000151
Figure FDA0002506553440000161
Figure FDA0002506553440000171
Figure FDA0002506553440000181
Figure FDA0002506553440000191
Figure FDA0002506553440000201
Figure FDA0002506553440000211
Figure FDA0002506553440000221
Figure FDA0002506553440000231
Figure FDA0002506553440000241
Figure FDA0002506553440000251
Figure FDA0002506553440000261
Figure FDA0002506553440000271
Figure FDA0002506553440000281
Figure FDA0002506553440000291
Figure FDA0002506553440000301
3. the organic electroluminescent element as claimed in claim 1 or 2, wherein the organic film is formed by a vacuum deposition method or a solution process.
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