KR101181270B1 - Compound Containing Indoloacridine And Organic Electronic Element Using The Same, Terminal Thereof - Google Patents

Abstract

The present invention provides a compound containing liposonodololoquinoline, an organic electric device using the same, and a terminal thereof.

Description

Compound Containing Indoloacridine And Organic Electronic Element Using The Same, Terminal Thereof}

The present invention relates to a compound containing iodine indoloquinoline, an organic electric device using the same, and a terminal thereof.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. The principle is that when a small amount of dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high-efficiency light. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

The present inventors have found a compound containing iodine indoloquinoline having a novel structure, and also found that when the compound is applied to an organic electric device, the luminous efficiency, stability and lifespan of the device can be greatly improved.

Accordingly, an object of the present invention is to provide a novel compound containing iodine indoloquinoline, an organic electric device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound of the formula

The present invention may be useful as a hole injection material, a hole transport material, a light emitting material and / or an electron transport material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, white, etc. according to a compound containing iodine indoloquinoline. Can be. In addition, the present invention may be useful as a host material and a major transport material for phosphorescent dopants of various colors, depending on the compound containing iodine indoloquinoline.

The present invention also provides an organic electronic device using the compound having the above formula and a terminal including the organic electronic device.

Compounds containing iodine indoloquinoline can play a variety of roles in organic electronic devices and terminals, and are suitable for hole injection materials, hole transport materials, and light emitting materials suitable for fluorescent and phosphorescent devices of all colors such as red, green, blue, and white. And / or as electron transport materials. In addition, the compound containing phospho indoloquinoline may be useful as a host material and a hole transport material of phosphorescent dopants of various colors in the organic electronic device and the terminal.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected,""coupled," or "connected."

In one aspect, the present invention provides a compound of Formula 1 below.

In the above formula,

(1) L is a hydrogen atom; Halogen atom; Cyano; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si). Is selected.

(2) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently of each other a hydrogen atom; A halogen atom; Cyano group; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si). Is selected.

(3) R ₂ to R ₉ may be bonded to an adjacent group to form a substituted or unsubstituted ring.

(4) n is an integer of 1-4.

(5) The compound having the above structural formula can be used in a soluble process.

In another aspect, the present invention provides a compound of Formula 2 below.

In the above formula,

(6) Ar is a hydrogen atom; Halogen atom; Cyano; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si). Is selected.

(7) R may be the same as defined in (2) above.

In another aspect, the present invention provides a compound of formula 3 below.

In the above formula,

(8) Ar may be the same as formula (2).

(9) R ₁₀ and R ₁₁ are each independently a hydrogen atom; A halogen atom; Cyano group; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si). Is selected.

In this case, the compounds represented by Formulas 2 and 3 may also be used in the solution process (soluble process). In addition, Formulas 2 and 3 are represented by the formula (1) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ is a hydrogen atom when compared to the formula (1) It should be understood that for simplicity, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are omitted.

Specific examples of the compounds belonging to Formulas 1 to 3, which are compounds containing iodine indoloquinoline, according to an embodiment of the present invention, include the compounds of Formula 4 below, but the present invention is not limited thereto.

Various organic electric devices exist in which compounds including iodine indoloquinoline described with reference to Chemical Formulas 1 to 4 are used as the organic material layer. Examples of organic electroluminescent devices in which compounds including iodine indoloquinoline described with reference to Chemical Formulas 1 to 4 may be used include organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, and organic transistors. (Organic TFT), photodiode, organic laser, laser diode and the like.

As an example of the organic electroluminescent device (OLED) that can be applied to the compound containing the yisoindoloquinoline described with reference to Formula 1 to 4 will be described below, the present invention is not limited to this various organic electroluminescent device To the compound comprising the above-described iodine indoquinoline can be applied.

Another embodiment of the present invention is an organic electric device comprising a first electrode, a second electrode and an organic material layer disposed between these electrodes, wherein at least one layer of the organic material layer comprises an organic electric field comprising the compounds of Formulas 1 to 4 Provided is a light emitting device.

1 to 6 show examples of the organic light emitting display device to which the compound of the present invention can be applied.

The organic light emitting device according to another embodiment of the present invention, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer And a structure known in the art using conventional manufacturing methods and materials in the art, except that at least one layer of the organic material layer including the electron injection layer is formed to include the compounds of Formulas 1 to 4. It can be prepared as.

The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode. Although not shown, the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound containing phospho indoloquinoline described with reference to Formulas 1 to 4 may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer. Specifically, the compound containing phospho indoloquinoline described with reference to Chemical Formulas 1 to 4 may include at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, and a protective layer. It may be used instead or in combination with them. Of course, the organic layer may be used not only in one layer but also in two or more layers.

Compounds containing iodine indoloquinoline described with reference to Chemical Formulas 1 to 4 may play various roles in organic electric devices and terminals, and may be appropriately injected with fluorescence and phosphorescent devices of all colors such as red, green, blue, and white. It is useful as a material, a hole transport material, a light emitting material and / or an electron transport material.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

The organic electroluminescent device according to another embodiment of the present invention may form an organic material layer, for example, a light emitting layer or a transport layer by the soluble process of the compound containing the above-described iodine indoloquinoline.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used. When the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

As described above, a hole injection material, a hole transport material, a light emitting material, suitable for fluorescence and phosphorescent devices of all colors, such as red, green, blue, white, etc., according to the compound containing iodine indoloquinoline described with reference to Chemical Formulas 1 to 4 It may be used as an electron transport material and an electron injection material, and may be used as a host material for light emitting dopants of various colors.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

Meanwhile, the present invention includes a display device including the organic electric element described above, and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention described above may be a mobile communication terminal such as a mobile phone, and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote control, a navigation device, a game machine, various TVs, various computers, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. However, the following Preparation Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, the preparation or synthesis examples of the compounds containing the iodine indoquinoline belonging to the formula (4). However, since a large number of compounds containing iodine indoloquinoline belonging to the general formula (4) will be described by way of example one or two of the compounds containing iodine indoquinoline belonging to the general formula (4). Those of ordinary skill in the art, that is, those skilled in the art can prepare a compound including iodine indoloquinoline belonging to the present invention not illustrated through the preparation examples described below.

Intermediate synthesis method

Step 1) Synthesis of Intermediate A

[Reaction Scheme 1]

The starting material, 5-Bromoisoquinoline, was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (1.6 M in hexane) was slowly added dropwise, and the reaction was stirred for 30 minutes. The temperature of the reaction was lowered to -78 ° C and Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ , a small amount of water in the reaction was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated using column chromatography to obtain desired intermediate A. (Yield 73%).

Step 2) Synthesis of Intermediate B-1

Scheme 2

The intermediate A, 1-Bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in step 1) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate B-1 (yield: 67%).

Step 3) Synthesis of Intermediate B-2

Scheme 3

The intermediate A, 2,5-Dibromonitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in step 1) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate B-2 (yield: 61%).

Step 4) Synthesis of Intermediate B-3

Scheme 4

The intermediate A, 2,4-Dibromonitrobenzene, Pd (PPh ₃ ) ₄ , and K ₂ CO ₃ synthesized in step 1) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired intermediate B-3 (yield: 66%).

Step 5) Synthesis of Intermediate C-1

Scheme 5

Intermediate B-1 and triphenylphosphine synthesized in step 2) were dissolved in o- dichlorobenzene and refluxed for 24 hours. After completion of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired intermediate C-1 (yield: 53%).

Step 6) Synthesis of Intermediate C-2

[Reaction Scheme 6]

Intermediate B-2 and triphenylphosphine synthesized in step 3) were dissolved in o- dichlorobenzene and refluxed for 24 hours. At the end of the reaction, the solvent was removed using distillation under reduced pressure, and the concentrated product was separated using column chromatography to obtain the desired intermediate C-2 (yield: 48%).

Step 7) Synthesis of Intermediate C-3

[Reaction Scheme 7]

Intermediate B-3 and triphenylphosphine synthesized in step 4) were dissolved in o- dichlorobenzene and refluxed for 24 hours. At the end of the reaction, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired intermediate C-3 (yield: 50%).

Step 8) Synthesis of Intermediate D-1

[Reaction Scheme 8]

The intermediate C-2 and Phenylboronic acid, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in step 6) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product by column chromatography to give the desired intermediate D-1 (yield: 67%).

Step 9) Synthesis of Intermediate D-2

Scheme 9

The intermediate C-3 and Phenylboronic acid, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ synthesized in step 7) were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product using column chromatography to give the desired intermediate D-2 (yield: 62%).

Step 10) Synthesis of Intermediate E-1

[Reaction Scheme 10]

Intermediate C-2 and Iodobenzene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 6) were dissolved in toluene and then stirred at 110 ° C. for 12 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product by column chromatography to give the desired intermediate E-1 (yield: 69%).

Step 11) Synthesis of Intermediate E-2

[Reaction Scheme 11]

The intermediate C-3 and Iodobenzene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 7) were dissolved in toluene solvent and stirred at 110 ° C. for 12 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the resulting product by column chromatography to give the desired intermediate E-2 (yield: 65%).

Synthesis Example 1 Synthesis of Compound 13

[Reaction Scheme 12]

The intermediate C-1 and Iodobiphenyl, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 5) were dissolved in toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removal of a small amount of water with anhydrous MgSO ₄ and filtration under reduced pressure, the organic solvent was concentrated to give the desired compound 13 by column chromatography (yield: 56%).

Synthetic example  2: synthesis of compound 28

Scheme 13

Intermediate C-1 and 2-Chloro-4,6-diphenyl-1,3,5-triazine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 5) were toluene After dissolving in a solvent, it was stirred at 110 ℃ for 24 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 28 using column chromatography (yield: 42%).

Synthetic example  3: Synthesis of Compound 39

[Reaction Scheme 14]

Intermediate D-1 and 4-Bromo-2,6-diphenylpyridine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 8) were dissolved in toluene solvent and then at 110 ° C. Stir for 24 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 39 using the column chromatography (yield: 43%).

Synthetic example  4: Synthesis of Compound 70

[Reaction Scheme 15]

Intermediate D-2 synthesized in step 9) and 2- (4-Bromophenyl) -1-phenyl-1 H -benzo [ d ] imidazole, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu was dissolved in toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired product 70 by column chromatography (yield: 45%).

Synthetic example  5: Synthesis of Compound 84

[Reaction Scheme 16]

Intermediate E-1 and Dibiphenyl-4-ylamine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu synthesized in step 10) were dissolved in toluene and then stirred at 110 ° C. for 24 hours. I was. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired product 84 by column chromatography (yield: 44%).

Synthetic example  6: Synthesis of Compound 102

[Reaction Scheme 17]

Intermediate E-2 synthesized in step 11) and N- (Biphenyl-4-yl) -9,9-dimethyl-9 H -fluoren-2-amine, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t Bu was dissolved in toluene solvent and stirred at 110 ° C. for 24 hours. After the reaction was completed, the reaction was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. After removing a small amount of water with anhydrous MgSO ₄ and filtered under reduced pressure, the organic solvent was concentrated to give the desired compound 102 by using column chromatography (yield: 42%).

Of organic light emitting device  Manufacturing evaluation

Various compounds obtained through synthesis were used as light emitting host materials and hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting display device according to a conventional method.

First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm.

When measured as a luminescent host material, 30 nm of 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as a-NPD) as a major transport compound on this film was measured. Vacuum deposition was carried out to a thickness of to form a hole transport layer. After the hole transport layer was formed, tris (2-phenylpyridine) iridium (abbreviated as I r (ppy) ₃ hereinafter) was added as a phosphorescent Ir metal complex dopant on the hole transport layer. At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 5% by weight. (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was formed into an injection layer to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, Al was deposited to a thickness of 150 nm, and the organic light emitting device was manufactured by using this Al / LiF as a cathode.

When measuring as a hole transport layer material, a light emitting material doped with BD-052X (Idemitus) 7% doped with a thickness of 45 nm was used. In this case, BD-052X is a blue fluorescent dopant, and an organic light emitting diode was manufactured using 9,10-di (naphthalen-2-yl) anthracene (ADN) as a light emitting host material.

Comparative Experimental Example 1

Compounds 13, 28, 39, or 70 in the synthesized compounds were used as light emitting host materials for the organic electric devices described above, to fabricate the organic light emitting diodes of Examples 1 to 4.

For comparison, an organic electroluminescent device having the same structure as the test example was manufactured using a compound represented by Formula 5 (hereinafter abbreviated as CBP) as a light emitting host material instead of the compound of the present invention.

Emitting layer
Host material Voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1 Compound 13 5.5 0.30 50.5 (0.31, 0.61) Example 2 Compound 28 4.3 0.32 67.1 (0.32, 0.61) Example 3 Compound 39 4.8 0.31 55.7 (0.31, 0.60) Example 4 Compound 70 4.7 0.32 61.4 (0.31, 0.60) Comparative Example 1 CBP 6.1 0.31 32.6 (0.33, 0.61)

Comparative Experiment 2

In addition, the organic electroluminescent devices of Examples 4 and 5 were prepared using Compound 84 or 102 as the hole transport layer material of the organic electric device described above.

For comparison, an organic electroluminescent device having the same structure as the test example was manufactured by using the compound represented by Formula 8 (hereinafter abbreviated as a-NPD) as a hole transport material instead of the compound of the present invention.

Emitting layer
Host material Voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 4 Compound 84 6.7 13.11 9.0 (0.15, 0.14) Example 5 Compound 102 6.1 12.74 9.6 (0.15, 0.15) Comparative Example 1 a-NPB 7.2 13.35 7.5 (0.15, 0.15)

As can be seen from the results of Table 1 and Table 2, the organic light emitting device using the material for the organic light emitting device is not only improved in efficiency and color purity but also driving voltage is significantly higher than CBP and a-NPD used as comparative examples. Can be improved. Therefore, since green and blue light emission of long life is obtained, it is used as a green phosphorescent host material and a hole transport layer material of the organic light emitting device, and thus it is possible to remarkably improve the luminous efficiency and lifetime.

It is apparent that the same effects can be obtained even when the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, the host material and the hole transport layer of the light emitting layer, as well as the electron injection layer, the electron transport layer and the hole injection layer.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments.

The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (12)

A compound represented by the following formula (1).
[Formula 1]

In Chemical Formula 1,
(1) L is a hydrogen atom; A halogen atom; Cyano group; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si). Selected,
(2) R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently of each other a hydrogen atom; A halogen atom; Cyano group; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) and silicon (Si). Selected,
(3) n is an integer of 1 to 4,
(5) R ₂ to R ₉ may be bonded to an adjacent group to form a substituted or unsubstituted ring.
(If n = 1, except that R ₁ to R ₉ are all hydrogen and L is an aryl group or heteroaryl group) The method of claim 1,
R ₂ to R ₉ combine with an adjacent group to form a substituted or unsubstituted ring. A compound represented by the following formula (2).
(2)

In Formula 2,
Ar and R are each independently of one another,
Hydrogen atom; A halogen atom; Cyano group; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si). Is selected. However, the case where R is hydrogen and Ar is an aryl group or heteroaryl group is excluded. The method according to claim 1 or 3,
The compound of Formula 1 or Formula 2 is one of the following compounds.

The compound represented by the following formula (3).
(3)

In Chemical Formula 3,
Ar, R ₁₀ and R ₁₁ are each independently of the other,
Hydrogen atom; A halogen atom; Cyano group; Thiol group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms; Substituted or unsubstituted C2-C60 alkenyl group; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms; Substituted or unsubstituted C1-C50 heteroalkyl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); Substituted or unsubstituted C1-C60 heteroaryl group containing at least one of sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si); And a substituted or unsubstituted heteroaryloxy group having 1 to 60 carbon atoms containing at least one sulfur (S), nitrogen (N), oxygen (O), phosphorus (P) or silicon (Si). Is selected. 6. The method of claim 5,
The compound of Formula 3 is one of the following compounds.

An organic electric device comprising at least one organic material layer comprising the compound of claim 1 or 5. 8. The method of claim 7,
And forming the compound into the organic material layer by a soluble process. 8. The method of claim 7,
An organic electroluminescent device comprising a first electrode, one or more organic material layers, and a second electrode, which are sequentially stacked. 8. The method of claim 7,
The organic material layer is an organic electroluminescent device comprising a light emitting layer or a hole transport layer. An electronic device comprising the organic electric device of claim 7;
And a control unit for driving the electronic device. 12. The method of claim 11,
The organic electroluminescent device includes an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic transistor (organic TFT), a photodiode, an organic laser, and a laser diode. Terminal) characterized in that one of.

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