KR100428642B1 - Organic material having double spiro structure - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a double spiro type organic compound, and in particular, has a high melting point, high quantum efficiency, can control the mobility of a carrier, and an electric device such as an organic light emitting device. The present invention relates to a double spiro type organic compound having a structure capable of improving the performance of a hole transporting material, a light emitting material, a fluorescent dye, and an electron transporting material.

The present invention provides a double spiro type compound represented by the following formula (1):

[Formula 1]

The novel organic compounds of the present invention have a double spiro structure exhibiting a high melting point for derivatives derived from Formula 1, and by introducing appropriate substituents, fluorescent materials used in hole transport materials, light emitting materials, electron transport materials or light emitting layers Dopant properties can be imparted, and the device's drive life and thermal stability can be improved when the device is fabricated from these materials.

Description

Double Spiro Organic Materials {ORGANIC MATERIAL HAVING DOUBLE SPIRO STRUCTURE}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a double spiro type organic compound, and in particular, has a high melting point, high quantum efficiency, can control the mobility of a carrier, and an electric device such as an organic light emitting device. The present invention relates to a double spiro type organic compound having a structure capable of improving the performance of a hole transporting material, a light emitting material, a fluorescent dye, and an electron transporting material.

The organic light emitting device uses a principle of forming a thin film of organic material between two electrodes (anode and cathode) to receive and transport holes and electrons injected from each electrode, and to generate light by recombining the injected holes and electrons. . Such an organic light emitting device can improve the life and efficiency of the device by appropriate selection of the electrodes and organic materials used. Also, when manufacturing devices, full color displays can be manufactured by forming red, green, and blue pixels using shadow masks.

The performance of the organic light emitting device has been improved by forming an organic thin film having a two-layer structure disclosed in U.S. Patent No. 4,359,507, and recently, a hole injection layer for receiving holes from an anode, a hole transporting layer for transporting holes, and a combination of holes and electrons By using the four-layer structure of the light emitting layer that emits light and the electron transporting layer that receives electrons from the cathode and transfers them to the light emitting layer, an efficient device is manufactured. At this time, the organic materials forming each layer should have stability to electrons, holes or electrons, and holes depending on their role, and it is a general requirement to form an amorphous uniform film when forming a thin film. In addition, it can be used practically only when it is stable against heat generated during driving or high external temperature.

This thermal stability is better with higher glass transition temperatures of the materials used. On the other hand, when the molecular weight is increased to increase the glass transition temperature, there is a problem in that vacuum deposition becomes difficult. Therefore, it is important to maintain the sublimability of the material required for vacuum deposition while increasing the glass transition temperature.

A common method used to achieve this purpose is to introduce aromatic or heterocyclic groups into the materials of use. Increasing the number of non-aromatic saturated hydrocarbons results in relatively low sublimation. However, introducing an aromatic group with a flat structure into the molecule deepens the pi-orbital overlap between the molecules, thereby reducing the efficiency of trap and luminous that inhibits carrier transport. Factors that hinder device performance, such as quenching sites or excimer formation by interaction between molecular orbitals in an excited state, are likely to occur.

Conventionally used materials have various chemical structures depending on their role. As a hole injection material for injecting holes, a compound having excellent thermal stability while maintaining a stable interface with an anode is used. For example, a porphyrin-based copper complex disclosed in US Patent No. 4,356,429 (Kodak) copper phthalocyanine (hereinafter referred to as CuPc).

The hole transporting material that plays a role of transporting holes is most representative of aryl amines in which aromatic rings are variously substituted around nitrogen atoms. It is most widely used because of its high hole transport speed and excellent electrical stability to holes. In order to increase the thermal stability of such aryl amine-based materials, several aryl amines may be introduced into one molecule or naphtyl substituents may be introduced instead of phenyl substituents (US Pat. No. 5,554,450). Representative examples include 4,4'-bis- [N- (1-naphthyl) -N-phenyl-amino] biphenyl (4,4'-bis [containing a naphthyl group;N-(1-naphtyl)-N-phenyl-amino] biphenyl; Hereinafter referred to as NPB). Recently, a hole transport material having a high glass transition temperature by substituting such an aryl amine-based material into a spiro structure has been known (US Pat. No. 5,840,217).

8-hydroxyquinoline aluminum salt (Alq3) is the most stable material and emits green light. It is used as.

In recent years, as the production of a color display device has emerged as a concern of the display industry, development of a blue light emitting material has been actively performed. Compared with Alq3, which is an organic metal-based green emitter, blue emitters generally have a low melting point and a short lifetime. Representative blue light emitting materials used are aromatic hydrocarbon materials disclosed in US Pat. Nos. 5,516,577 and 5,366,811. Aromatic hydrocarbon materials having such specific structures have long been known to exhibit fluorescence and are widely used in the industry for applications such as fluorescent brighteners.

In order for a blue light emitting material containing such an aromatic hydrocarbon to be properly applied to an organic light emitting device, thin film deposition is possible only when both a high glass transition temperature and a sublimation property are combined. Recently, blue emitters having a spiro form with improved thermal stability have been developed (US Pat. No. 5,840,217). Spiro-shaped materials centering on the two pentagons introduce various substituents into two biphenyl groups orthogonal to each other at an angle of 90 degrees in space to form a blue light-emitting body.

Another example of a blue light emitter is an organometallic compound containing aluminum published by Kodak, USA, a heterocyclic organic compound using imidazole groups, and an organic compound containing fused aromatic groups. And the like (US Pat. Nos. 5,150,006, and 5,645,948).

In order to increase the efficiency of the organic light emitting device, excitons in which the holes and electrons delivered to the light emitting layer are recombined in the fluorescent dye or recombined in the material forming the light emitting layer by doping a small amount of fluorescent dye in the light emitting layer are energy. Energy transfer may also serve to emit light (US Pat. No. 4,769,292). In this case, the energy band gap of the fluorescent dye should be similar to or smaller than the energy band gap of the material hosting the fluorescent dye. Depending on the selection of the appropriate host material and the fluorescent dye, and the concentration of the appropriate fluorescent dye, light emission corresponding to the band-gap of the fluorescent dye can be obtained.

Here, most of the fluorescent dyes form an excimer due to overlapping molecular trajectories of the dyes when the concentration is too high, so that the luminous efficiency is drastically lowered or the emission wavelength is shifted. This is because the molecular structure of a typical fluorescent dye has a planar structure consisting of a pi-orbital skeleton. Examples include blue fluorescent dyes perylene, anthracene, green fluorescent dyes quinacridone, coumarine, and derivatives thereof, and fluorescent dyes for yellow light emission, rubrene ( rubrene), red fluorescent dye Nile Red, DCM, and derivatives thereof.

The electron transporting material which receives electrons from the cathode and delivers them to the light emitting layer should form a stable interface with the material forming the electrode and transport the electrons at a high speed. Like other materials constituting the organic light emitting device, the electron transporting material must have a high vitrification transition temperature because it must be stable to heat generated during device driving or storage. In addition, it is necessary to transport electrons well and at the same time stable electrical stability to the electrons. For this reason, Alq3, which is used as a green fluorescent material, is also used as a representative electron transport material.

SUMMARY OF THE INVENTION In view of the problems of the prior art, an object of the present invention is to provide a novel organic material having a high melting point, high quantum efficiency, and capable of controlling the mobility of a carrier.

Another object of the present invention can be commonly used in organic materials such as hole transport material, light emitting material, fluorescent dye, electron transport material constituting an electric device such as an organic light emitting device, or organic materials that can improve the performance of each organic material To provide.

Still another object of the present invention is to provide an organic material having high thermal stability, easy introduction of functional groups as necessary, and a chemical structure capable of minimizing intermolecular overlap.

Still another object of the present invention is to provide an organic material having a high melting point and capable of maintaining the sublimation necessary for the deposition process.

It is another object of the present invention to provide an organic material which maintains high quantum efficiency required for a luminescent material or a fluorescent dye.

It is still another object of the present invention to provide an organic material which is included in an organic light emitting device to improve the life of the device and that can greatly improve the color of the total color display, in particular, the color of blue.

It is still another object of the present invention to provide an organic material which can be synthesized with various derivatives and can be usefully used to control the change in emission wavelength or desired electrical properties.

It is still another object of the present invention to provide an element that requires high quantum efficiency, an element that requires the transfer of electrons or holes, an optical photo conductor (OPC) drum used in a solar cell or a copier or a laser printer made of organic materials, or an organic transistor. To provide an organic material that can be used (organic transistor) and the like.

1 is a simplified cross-sectional view of an organic light emitting device used as an example of the present invention.

2 is a simplified cross-sectional view of an organic light emitting device having a finely divided organic layer structure.

Reference numeral 1 is a substrate, 2 is an anode, 3 is a cathode, 4 is a hole transport layer, 5 is an electron transport layer, 6 is a hole injection layer, and 7 is a light emitting layer.

The present invention provides a double spiro type compound represented by the following formula (1) to achieve the above object:

[Formula 1]

In the formula of Formula 1,

R ¹ to R ²⁴ are the same as or different from each other, provided that R ¹ to R ²⁴ are not all hydrogen atoms or halogens,

At least one of R ¹ to R ²⁴

One or more unsubstituted or substituted with X substituents as defined below

Aliphatic hydrocarbons having 1 to 20 carbon atoms; An alkoxy group; Arylamine groups; Aromatic hydrocarbons; Nitrile (-CN); Acetylene groups;

Heterocyclic compounds selected from the group consisting of thiazole, oxazole, imidazole, and thiophene; or

Substituent which is a moiety of the compound represented by Formula 1,

The rest are hydrogen; Or a halogen group selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I),

In addition, R ¹⁰ and R ¹¹ , or R ¹⁴ and R ¹⁵ , or R ¹⁰ and R ¹¹ and R ¹⁴ and R ¹⁵ may be bonded to each other to form an aromatic ring or a heterocyclic ring,

The X substituent is

Hydrogen; Halogen groups of fluorine, chlorine, bromine or iodine; aliphatic hydrocarbons having 1 to 20 carbon atoms; An alkoxy group; Arylamine group; Aromatic hydrocarbons; Nitrile group (-CN); Acetylene group; Heterocyclic compounds of thiazoles, oxazoles, imidazoles, or thiophenes; Or a moiety of the compound represented by Formula 1 above.

Hereinafter, the present invention will be described in detail.

First, an organic light emitting device to which a double spiro type compound represented by Chemical Formula 1 of the present invention is applied as an example will be described.

A simple diagram of an organic light emitting device applied to the present invention is shown in FIG.

In FIG. 1, the layer 1 is a substrate supporting the anode 2, and glass, plastic, non-conductive metal, ceramic, or the like may be used. In order to use a conductive metal as layer 1, an electrical insulator must be used between the layer 1 and the conductive anode layer 2.

The anode layer 2 is electrically shorted by an organic material from the cathode layer 3, which is the opposite electrode, and the anode materials used are indium tin oxide, indium zinc oxide, and tin oxide. Transparent electrodes such as tin oxide and fluorinated tin oxide may be used. In the case where the light generated in the organic device does not need to pass through the layer 1, a metal electrode may be used. However, in common with the transparent electrode exemplified above, a material having a high work function is selected. desirable. If a positive work function anode is used, hole injection from the anode to the layer 4 of the hole transport material can be facilitated when driving the device by applying a forward electric field.

The layer 4 which interfaces with the anode layer 2 serves as a hole transport layer to receive holes from the anode and transport holes in the direction of the cathode. Between the hole transport layer 4 and the cathode layer 3, an electron transport layer 5 for receiving electrons from the cathode and transporting electrons in the direction of the anode is located. Depending on the hole transport layer and the type of the electron transport layer used, the recombination position of electrons and holes may be selected from the layers 4 and 5.

The material constituting the negative electrode layer 3 is selected from materials having a low work function, and examples thereof include aluminum (Al), magnesium (Mg), silver (Ag), calcium (Ca), and lithium (Li). Magnesium and silver (Mg: Ag) or a mixture of lithium and aluminum (Li: Al), or a thin film (1 to 20 kPa) of lithium fluoride and aluminum (LiF / Al) or lithium oxide and aluminum (Li ₂ O / Al It may be a two-layer electrode consisting of). The cathode having a low work function applies a forward electric field to facilitate electron injection from the cathode to the electron transport layer 5 when driving the device.

The organic light emitting device shown in FIG. 2 is similar to the organic light emitting device of FIG. 1, but subdivids the organic material layer between the two electrode layers 2 and 3. In FIG. 2, layer 1, layer 2 and layer 3 represent a substrate, an anode and a cathode layer, respectively, as shown in FIG. 1, and layer 6, layer 4, layer 7 and layer 5. ) Represent a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, respectively.

In order to improve the luminance, driving voltage, lifespan, etc. of the organic light emitting diode, as shown in FIG. 2, the hole injection layer and the light emitting layer may be added simultaneously or separately. In FIG. 2, the hole injection layer 6, which interfaces with the anode layer 2, forms a stable interface with an anode material made of an inorganic oxide, a metal, or a conductive polymer, and smoothly injects holes from the anode to be transferred to the hole transport layer. Play a role. In FIG. 2, the light emitting layer 7 positioned between the hole transport layer 4 and the electron transport layer 5 is a layer in which holes and electrons injected from the anode and the cathode recombine to emit light, and are made of a material having high quantum efficiency. .

In addition to the structures illustrated in FIGS. 1 and 2, the organic material layer between the two electrodes may be further subdivided to improve the performance of the device.

In the present invention, in the organic material positioned between two electrodes of the representative organic light emitting device shown in FIGS. 1 and 2, the compounds represented by the above Chemical Formula 1 may be used, respectively or simultaneously.

Hereinafter, a compound of the double spiro form of Chemical Formula 1 will be described.

In the compound represented by Formula 1, a compound in which all of R ¹ to R ²⁴ are substituted with hydrogen atoms is a known compound synthesized for the dehydration reaction of aromatic carbinol (J. Am. Chem. Soc. , 52, 2881 , 1930). Compounds provided in the present invention, by introducing a variety of substituents using only a double spiro skeleton in the known compounds to provide thermal stability, luminous efficiency, device life, etc. required in electrical devices such as organic light emitting devices It is to help improve.

Representative examples of the aromatic hydrocarbon which may be a substituent of R ¹ to R ²⁴ are as follows.

, , ,

, , ,

, .

Substituents of the aromatic hydrocarbons exemplified above may in turn have one or more secondary substituents represented by X, examples of which include hydrogen atoms; Aliphatic hydrocarbons having 1 to 20 carbon atoms; Halogen groups such as fluorine, chlorine, bromine and iodine; An alkoxy group; Arylamine groups; Aromatic hydrocarbons; Heterocyclic compounds such as thiazole, oxazole and imidazole; Nitrile (-CN); Acetylene groups; Or it may be a substituent selected from the group containing the residue of the compound represented by the formula (1), they may also be fused with a heterocyclic ring of the primary substituent (fused) to form a fused ring (fused ring).

In addition, representative examples of the heterocyclic compound and the aryl amine group which may be a substituent of the R ¹ ~ R ²⁴ are as follows.

, , ,

, , ,

, , ,

, , .

The heterocyclic substituents exemplified above may in turn have one or more secondary substituents represented by the above X, examples of which are the same as the secondary substituents X of the aromatic hydrocarbon substituent.

Structural characteristics of the organic compound that can be applied to the organic light emitting device provided by the present invention can be described from the formula (1a).

[Formula 1a]

As illustrated in the embodiment of the present invention, when all of the substituents R ¹ to R ²⁴ of the organic material represented by Chemical Formula 1 are substituted with a hydrogen atom, as another expression, in Formula 1a, A and A When all of the phenyl groups constituting ', B, B' are substituted with hydrogen atoms, the organic light emitting device using the same requires a high driving voltage. In order to lower the driving voltage and increase the luminous efficiency or to impart the hole transporting ability or the electron transporting ability, it is necessary to substitute the carbon atoms of the phenyl groups represented by A, A ', B, and B' simultaneously or independently. need.

In the space, the planes of the phenyl groups constituting A and A 'and the planes of the phenyl groups constituting B and B' are orthogonal to each other. It takes up about twice as much space. This feature can be used to minimize excimer formation due to molecular orbital overlap between molecules.

For example, the molecular orbits of the light emitters positioned at B and B 'in space by introducing the substituents constituting the appropriate A and A' and the substituents serving as light emission simultaneously or independently of each other. You can minimize your loyalty. In order to prevent molecular orbital overlap of an effective light emitter, an alkyl group (C ₁ to C ₂₀ ) may be introduced to A and A ′, or a functional group may be introduced to minimize intermolecular overlap in other spaces. If the excimer is not formed even when the molecule is overlapped, or the effect of the excimer formation is insignificant or positive, a substituent having luminescence may be introduced into the phenyl groups A and A '.

In order to impart hole transporting ability to the molecule represented by Formula 1, phenyl groups A, A ', B, and B' may be given at the same time or independently with substituents having hole transporting capacity, for example, aryl amine groups. It can improve the hole transport ability to the molecule.

Another method for increasing the luminous efficiency of the organic light emitting device is a method of optimizing the equilibrium of holes and electron concentration in the device. Carriers of excessive concentrations do not contribute to light emission, thereby reducing the quantum luminous efficiency and shortening the lifetime of the device. This optimization of carrier concentration can be achieved by proper selection of the electrode and oxidation, reduction levels of the organic materials present between the two opposite electrodes, and carrier mobility. In addition, the recombination position of the carriers may be a factor that determines the lifetime of the organic light emitting device.

Therefore, the appropriate structural transformation of the organic materials used, in particular, the possibility of changing the moving speed, oxidation, or reduction level of the carrier is essential for efficient and stable device fabrication. This object can be achieved by the material represented by the formula (1) used in the present invention.

In the structure of Formula 1a, a desired property may be obtained by introducing a substituent which may increase or decrease the mobility of electrons or holes in the phenyl groups A, A ', B, and B', and the mobility of such carriers It is possible to introduce a functional group for controlling and a functional group for emitting light into one molecule at the same time.

Another method for increasing the luminous efficiency and lifetime of the device is to dope a small amount of fluorescent dye in the light emitting layer. Fluorescent dye used for doping uses a material having a similar or smaller energy band gap than the material constituting the light emitting layer. Electrons and holes recombined in the light emitting layer move to a fluorescent dye having a relatively small energy band gap, and emit light. A mainly used fluorescent dye forms an excimer at a high concentration, thereby decreasing quantum efficiency.

The material represented by the formula (1) used in the present invention suggests a way to solve this problem. Independently or simultaneously with the phenyl groups B and B ', luminescent functional groups having relatively small energy band gaps are introduced, and functional groups with large energy band gaps are introduced with phenyl groups A and A', thereby recombining the positions of B and B in the molecule. It can be limited to the position containing the phenyl group of ".

Examples of representative molecular structures using the above-mentioned concepts are examples of introducing a substituent having a hole transporting ability or a light emitting capability into the phenyl groups B and B ', as follows.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15] [Formula 16] [Formula 17] [Formula 18] [Formula 19] [Formula 20] [Formula 21] [Formula 22] [Formula 23] [Formula 24] [Formula 25] In addition, the compound of Formula 1 may introduce two or more double spiro structures in one molecule, and representative examples thereof are the compounds of Formula 26 and Formula 27 as follows.

[Formula 26]

[Formula 27]

When the compound of Formula 1 is described by the structure of Formula 1a, a substituent is introduced into the phenyl groups A and A 'to improve hole or electron transporting ability or an alkyl group is introduced to overlap the pi-orbital between molecules in space. It can be minimized, it can be used as a material to form a light emitting layer by introducing a light emitter. Representative examples thereof are the compounds represented by the following Chemical Formulas 28 to 33.

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

In addition, in the structure of Formula 1a, representative examples of the substituents of A and A 'and examples of the substituents of B and B' may be mixed to substitute A, A 'and B and B' at the same time. Representative examples of such compounds are compounds represented by the following Chemical Formula 34:

[Formula 34]

In addition, in the structure of Formula 1a, an appropriate linking group may be introduced into the phenyl groups B and B 'to synthesize a polymer in which the structure represented by Formula 1 is repeatedly represented.

Such polymer-type compounds may be used for spin-coating, roll-coating, screen-printing, ink-jet printing, etc., rather than vacuum deposition in the manufacture of organic light emitting devices. It is preferable to manufacture the device using the process of. As such, representative examples of the polymer in which the structure represented by Formula 1 is repeatedly represented are the compounds of Formulas 35 to 37 as follows.

N in the formulas of the compounds of Formulas 35 to 37 is an integer of 2 or more.

[Formula 35]

[Formula 36]

[Formula 37]

Examples of the compound that satisfies the general formula (1) presented above are merely presented in part for the purpose of understanding the present invention, and the compounds provided by the present invention are not limited thereto.

Since the compound of the present invention has various characteristics such as having a high melting point and excellent sublimation characteristics, it can be used as an element requiring high quantum efficiency, an element requiring an electron or hole transfer, or an organic substance in addition to the application of the organic light emitting element. The solar cell may be used in various ways such as an organic solar cell, a solar cell, an optical photo conductor (OPC) drum used in a copying machine or a laser printer, or an organic transistor.

Synthesis method of the compound satisfying the formula (1) and the manufacturing of the organic light emitting device using the same will be described in more detail by the following examples and comparative examples, these examples are intended to illustrate the present invention is not limited to these no.

EXAMPLE

Among the various various starting materials for the synthesis of new compounds satisfying Formula 1, the following starting materials were synthesized as an example.

Preparation Example 1

(Synthesis of starting material represented by Formula 38)

For the synthesis of the compound satisfying Formula 1, the starting material represented by Formula 38 was synthesized as follows.

[Formula 38]

5.0 g (21.5 mmol) of 2-Bromobiphenyl was dissolved in 50 mL of THF, cooled to -78 ° C, and then 32 mL (1.7 M in pentane) of tert-butyllithium (t-BuLi) was slowly added. Added dropwise.

After stirring for 1 hour at the same temperature, 3 g (8.2 mmol) of 2,6-dibromoanthraquinone was added and stirred for 30 minutes, and the reaction temperature was gradually raised to room temperature, followed by stirring for 4 hours. It was.

The reaction mixture was poured into a mixed solution of 30 ml of diethylether and 50 ml of 2N hydrochloric acid solution, stirred for 30 minutes, and the resulting solid was filtered, washed with water and diethylether and dried.

5.1 g of the dried solid sample was taken, dissolved in 60 ml of acetic acid, and then added with a catalytic amount (5 drops) of hydrochloric acid (35% aqueous solution) to reflux for 3 hours. The resulting solid compound was filtered, washed with acetic acid and dried to obtain 4.6 g of a white solid compound having a structure of Formula 38 (yield: 88%).

The NMR analysis results of the compound of Formula 38 prepared above are as follows.

¹ H NMR (300 MHz, DMSO-d ₆ ) d 8.12 (4H, d), 7.52 (4H, t), 7.32 (4H, t), 7.06 (4H, d), 6.84 (2H, d), 6.28 ( 2H, s), 6.16 (2H, d)

Preparation Example 2

(Synthesis of starting material represented by Formula 39)

For the synthesis of the compound satisfying Formula 1, the starting material represented by Formula 39 was synthesized as follows.

[Formula 39]

2.68 g (11.5 mmol) of 2-bromobiphenyl was dissolved in 35 mL of THF, and cooled to -78 ° C, followed by 16.9 mL (t-BuLi) of 16.9 mL (1.7 M in pentane). It was added dropwise and stirred for 40 minutes at the same temperature.

To the solution was added 1.44 g (5 mmol) of 2-bromoanthraquinone. After slowly raising the temperature to room temperature, the mixture was stirred for 3 hours.

The reaction mixture was poured into a mixed solution of 15 ml of diethylether and 25 ml of a 2N hydrochloric acid solution, stirred for 30 minutes, and the resulting solid was filtered, washed with water and diethylether, and dried.

2.5 g of the dried solid sample was taken, dissolved in 50 ml of acetic acid, and then added with a catalytic amount (10 drops) of concentrated sulfuric acid to reflux for 3 hours. The resulting solid compound was filtered, washed with acetic acid and dried to obtain 2.2 g of a white solid compound having the structure of Formula 39 (yield: 79%).

The NMR analysis results of the compound of Formula 39 prepared above are as follows.

¹ H NMR (300 MHz, CDCl ₃ ) d 7.9 (4H, m), 7.5-7.4 (4H, m), 7.3 (4H, t), 7.2 (4H, m), 6.9 (1H, d), 6.8 ( 2H, m), 6.5 (1H, s), 6.3 (2H, m), 6.2 (1H, d)

Example 1

In order to synthesize the compound represented by Chemical Formula 1, the compound represented by Chemical Formula 27 was synthesized using the compound represented by Chemical Formula 40 as a starting material.

[Formula 40] [Formula 27]

1.34 g (2.6 mmol) of the starting material represented by Formula 40 and 4,4'-di- (diethylphosphoylmethyl) -1,1'-biphenyl (4,4'-di- (diethylphosphorylmethyl) -1 0.5 g (1.3 mmol) of 1'-biphenyl) was dissolved in 80 mL of DMF, and 2.8 mL (1 M in ethanol) of lithium ethoxide was added dropwise at room temperature. After stirring for 12 hours at room temperature, the resulting solid compound was filtered, washed with water and ethanol and dried in vacuo.

The product represented by the formula (27) thus obtained was purified using a train sublimation method.

Elemental analysis and mass spectrometry of the obtained resultant represented by Chemical Formula 27 are as follows.

Elemental Analysis:

Theoretical value C (94.9%), H (5.02%) / Experimental value C (94.4%), H (5.12%)

Mass spectrometry:

Theoretical Value: 1162 / Experimental Value: 1163 [M + H] +

Example 2

In order to synthesize the compound of Formula 1, the compound represented by Formula 8 was synthesized using the compound represented by Formula 38 of Preparation Example 1 as a starting material.

1.34 g (6 mmol) of 2,2-diphenylvinylboronic acid, 0.36 g (0.75 mmol) of a starting material having a structure of Formula 27 of Preparation Example 1, Pd (PPh _{3 4} ) A mixed solution of 0.086 g (0.075 mmol), 10 mL of a 2N K ₂ CO ₃ aqueous solution, and 20 mL of toluene was refluxed for 24 hours.

The reaction solution was transferred to a sorting funnel at room temperature, and the organic layer was washed with water. The organic layer was separated and the solvent was removed under vacuum reduced pressure. 2 mL of chloroform was added to the resultant in the form of an oil, and then ethanol was added under stirring to obtain 4.2 g of a solid product having the structure of Formula 8 (yield: 75%).

Elemental analysis, mass spectrometry, and melting point of the resulting product represented by Chemical Formula 8 are as follows.

Elemental Analysis:

Theoretical value C (94.70%), H (5.30%) / Experimental value C (94.3%), H (5.4%)

Mass spectrometry:

Theoretical Value: 836 / Experimental Value: 837 [M + H] +

Melting point: 387.7 ° C.

Example 3

In order to synthesize the compound of Formula 1, the compound represented by Formula 29 was synthesized using the compound of Formula 39 of Preparation Example 2 as a starting material.

5.6 g (10.0 mmol) of the starting material having the structure of Formula 39 were dissolved in 60 ml of THF under a nitrogen atmosphere, and then 17.6 ml of t-BuLi; t-butyl lithium (1.7 M in pentane) at 78 ° C. The reaction solution was stirred for one hour, and then 4.5 ml of trimethylborate was added, stirring the solution for 3 hours while gradually raising the temperature to room temperature, and then adding an aqueous solution of hydrochloric acid at 1 N concentration of 150 ML was added and the solid solution was filtered, washed with water and dried in vacuo.

0.2 g of the resulting solid material was taken up in DMF and 0.06 g of 9,10-dibromoanthracene, 0.16 g of K ₃ PO ₄ , 12 mg of Pd (PPh ₃ ) ₄ It was added in turn. After raising the solution temperature to 60 ℃ and stirred for about 18 hours, the temperature of the solution was lowered to room temperature. 20 ml of ethanol was added to the cooled solution, and the precipitated solid was filtered after stirring for 30 minutes. The filtered solid was dissolved in 50 mL of NMP, passed through silica gel, the solvent was concentrated, and ethanol was added to give 0.16 g of a compound having the structure of Formula 26 as a white (yield: 41%), and a train sublimation method. It was further purified using.

Elemental analysis and mass spectrometry of the resulting product represented by the formula (26) are as follows.

Elemental Analysis:

Theoretical value C (95.2%), H (4.79%) / Experimental value C (94.9%), H (4.70%)

Mass spectrometry:

Theoretical Value: 1134 / Experimental Value: 1135 [M + H] +

Example 4

In order to synthesize the compound of Formula 1, the compound represented by Formula 10 was synthesized using the compound of Formula 39 of Preparation Example 2 as a starting material.

5.6 g of the starting material having the structure of Formula 39 was dissolved in 60 ml of THF under a nitrogen atmosphere, and then t-BuLi; 17.6 ml of t-butyl lithium (1.7 M in pentane) was added dropwise at 78 ° C. .

The reaction solution was stirred for one hour and then 4.5 ml of trimethylborate was added. After stirring for 3 hours while gradually raising the temperature of the solution to room temperature, 150 ml of 1N aqueous hydrochloric acid solution was added. After stirring the solution for 1.5 hours, the solid precipitate was filtered, washed with water and dried in vacuo.

0.52 g of the resulting solid material was taken up and dissolved in 10 ml of DMF under a nitrogen atmosphere, followed by 0.3 g of 9-bromo-10-phenylanthracene, 0.42 g of K ₃ PO ₄ , 35 mg of Pd (PPh ₃ ) ₄ was added sequentially. The temperature of the solution was raised to 60 ° C, then stirred for 12 hours, and cooled to room temperature. 20 mL of ethanol was added to the cooled solution and stirred for 30 minutes. The resulting solid was filtered, dissolved in 150 ml of chloroform, passed through silica gel to remove color, and dried in vacuo to yield 0.26 g of the compound having the structure of Formula 10 (yield: 35%), and train sublimation (train) further purification using the sublimation method.

Elemental analysis and mass spectrometry of the resulting product represented by the formula (10) are as follows.

Elemental Analysis:

Theoretical value C (95.0%), H (4.95%) / Experimental value C (94.9%), H (4.83%)

Mass spectrometry:

Theoretical Value: 732 / Experimental Value: 733 [M + H] +

In Comparative Example 1 and Examples 5 to 7, the following experiment was carried out to prove the suitability of the compounds satisfying the formula (1) to the device application, specifically the organic light emitting device application.

Comparative Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 kPa was washed by ultrasonic cleaning in an aqueous solution containing a cleaning agent, dried, and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

The hexanitrile hexaazatriphenylene represented by the following Chemical Formula 41 (HNHATP), which can lower the lifespan and the driving voltage of the device while acting as a hole injection on the prepared ITO transparent electrode, has a thickness of 500 Å. Thermal vacuum deposition was performed to form a hole injection layer.

[Formula 41]

NPB (600 kV), which is a material for transporting holes, is vacuum-deposited, and a compound having the structure represented by Chemical Formula 42 (R ¹ to R ²⁴ in Chemical Formula 1 is substituted with hydrogen in Chemical Formula 1), which serves as light emission, is 150. Vacuum deposition to a thickness of Å. Alq3 (400 kV), which serves as a transport and injection of electrons, was deposited on the light emitting layer to complete the formation of a thin film of an organic layer.

[Formula 42]

Lithium fluoride (LiF) and 2500 μm thick aluminum were sequentially deposited on the electron injection layer to form an electrode (cathode). In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, and the lithium fluoride was maintained at a deposition rate of 3 to 7 Å / sec for 0.2 Å / sec aluminum.

As a result of applying a forward electric field of 10.1 V to the fabricated organic light emitting diode, a blue spectrum of 57 nit brightness corresponding to x = 0.218 and y = 0.301 was observed based on a 1931 CIE color coordinate at a current density of 10 mA / cm 2.

Example 5

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 kPa was washed by ultrasonic cleaning in an aqueous solution containing a cleaning agent, dried, and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

CuPc (copper phthalocyanine) was thermally vacuum deposited to a thickness of 150 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (600 kV), which is a material for transporting holes, was vacuum deposited thereon, and a compound having the structure of Chemical Formula 16, which serves as light emission, was vacuum deposited to a thickness of 400 kPa. Alq3 (200 kV), which serves as a transport and injection of electrons, was deposited on the light emitting layer to complete the formation of a thin film of the organic layer.

Lithium fluoride (LiF) and 2500 μm thick aluminum were sequentially deposited on the electron injection layer to form an electrode (cathode). In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, and the lithium fluoride was maintained at a deposition rate of 3 to 7 Å / sec for 0.2 Å / sec aluminum.

As a result of applying a forward electric field of 9.1 V to the fabricated organic light emitting device, a blue spectrum of 126 nit brightness corresponding to x = 0.159 and y = 0.089 was observed based on a 1931 CIE color coordinate at a current density of 10 mA / cm 2.

Example 6

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 kPa was washed by ultrasonic cleaning in an aqueous solution containing a cleaning agent, dried, and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

HNHATP of Chemical Formula 41 was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (400 kPa), which is a material for transporting holes, was vacuum deposited thereon, and a compound having the structure of Chemical Formula 26 of Example 3, which serves as light emission, was vacuum deposited to a thickness of 300 kPa. Alq3 (300 nm) serving as a transport and injection of electrons was deposited on the light emitting layer to complete the formation of a thin film of the organic layer.

Lithium fluoride (LiF) and 2500 μm thick aluminum were sequentially deposited on the electron injection layer to form an electrode (cathode). In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was maintained at a deposition rate of 0.2 Å / sec, and aluminum was 3-7 Å / sec.

As a result of applying a forward electric field of 6.6 V to the fabricated organic light emitting diode, a blue spectrum of 254 nit brightness corresponding to x = 0.184 and y = 0.242 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2.

Example 7

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 kPa was washed by ultrasonic cleaning in an aqueous solution containing a cleaning agent, dried, and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

HNHATP of Chemical Formula 41 was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (400 kPa), which is a material for transporting holes, was vacuum deposited thereon, and a compound having the structure of Chemical Formula 10 of Example 4, which serves as light emission, was vacuum deposited to a thickness of 200 kPa. Alq3 (300 kV), which serves as a transport and injection of electrons, was deposited on the light emitting layer to complete the formation of a thin film of an organic layer.

Lithium fluoride (LiF) and 2500 μm thick aluminum were sequentially deposited on the electron injection layer to form an electrode (cathode). In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was maintained at a deposition rate of 0.2 Å / sec, and aluminum was 3-7 Å / sec.

As a result of applying a forward electric field of 6.7 V to the fabricated organic light emitting device, a blue spectrum of 168 nit brightness corresponding to x = 0.172 and y = 0.156 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed.

Example 8

In order to prove that the layer having the property of hole transport can be formed by selecting an appropriate substituent of the compound satisfying Formula 1, the following experiment was performed.

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 kPa was washed by ultrasonic cleaning in an aqueous solution containing a cleaning agent, dried, and then transferred to a plasma cleaner. The substrate was cleaned for 5 minutes using an oxygen plasma and then transferred to a vacuum evaporator.

HNHATP of Chemical Formula 41 was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. A compound having a structure of Formula 4 was vacuum deposited to a thickness of 400 kPa as a material for transporting holes thereon, and Alq3, which serves as light emission, electron transport, and electron injection, was vacuum deposited to a thickness of 600 kW. Lithium fluoride (LiF) and 2500 μm thick aluminum were sequentially deposited on the electron injection layer to form an electrode (cathode). In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was maintained at a deposition rate of 0.2 Å / sec, and aluminum was 3-7 Å / sec.

As a result of applying a forward electric field of 7.8 V to the fabricated organic light emitting diode, a green spectrum of 464 nit brightness corresponding to x = 0.326 and y = 0.550 was observed based on a 1931 CIE color coordinate at a current density of 10 mA / cm 2.

The novel organic compounds of the present invention have a double spiro structure exhibiting a high melting point for derivatives derived from Formula 1, and by introducing appropriate substituents, fluorescent materials used in hole transport materials, light emitting materials, electron transport materials or light emitting layers Dopant properties can be imparted, and the device's drive life and thermal stability can be improved when the device is fabricated from these materials.

Claims (38)

Double spiro compound represented by the following formula (1): [Formula 1] In the formula of Formula 1, R ¹ to R ²⁴ are the same as or different from each other, provided that R ¹ to R ²⁴ are not all hydrogen atoms or halogens, At least one of R ¹ to R ²⁴ One or more unsubstituted or substituted with X substituents as defined below Aliphatic hydrocarbons having 1 to 20 carbon atoms; An alkoxy group; Arylamine groups; Aromatic hydrocarbons; Nitrile (-CN); Acetylene groups; Heterocyclic compounds selected from the group consisting of thiazole, oxazole, imidazole, and thiophene; or Substituent which is a moiety of the compound represented by Formula 1, The rest are hydrogen; Or a halogen group selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I), Or R ¹⁰ and R ¹¹ , or R ¹⁴ and R ¹⁵ . Or R ¹⁰ and R ¹¹ and R ¹⁴ and R ¹⁵ may be bonded to each other to form an aromatic ring or a heterocyclic ring, The X substituent is Hydrogen; Halogen groups of fluorine, chlorine, bromine or iodine; Aliphatic hydrocarbons having 1 to 20 carbon atoms; An alkoxy group; Arylamine group; Aromatic hydrocarbons; Nitrile group (-CN); Acetylene group; Heterocyclic compounds of thiazoles, oxazoles, imidazoles, or thiophenes; Or a moiety of the compound represented by Formula 1 above. The method of claim 1, Compound of Formula 1 is a double spiro compound wherein at least one of R ¹ to R ²⁴ of the formula is a compound substituted with a substituent selected from the group of the following substituents: , , , , , , , . , , , , , , , , , , , And In the formula of the above substituents, each X is a hydrogen atom; Aliphatic hydrocarbons having 1 to 20 carbon atoms; Halogen groups of fluorine, chlorine, bromine or iodine; An alkoxy group; Arylamine groups; Aromatic hydrocarbons; Heterocyclic compounds of thiazole, oxazole, or imidazole; Nitrile (-CN); Acetylene groups; And it is a substituent selected from the group containing the residue of the compound represented by the formula (1), they can also be fused (fused) with the heterocyclic ring of the primary substituent (fused ring) to form a (fused ring). The method of claim 1, Double spiro compound represented by the following formula (2): [Formula 2] The method of claim 1, Double spiro compound represented by the following formula (3): [Formula 3] The method of claim 1, Double spiro compound represented by the following formula (4): [Formula 4] The method of claim 1, Double spiro compound represented by the following formula (5): [Formula 5] The method of claim 1, Double spiro compound represented by the following formula (6): [Formula 6] The method of claim 1, Double spiro type compound represented by the following formula (7): [Formula 7] The method of claim 1, Double spiro type compound represented by the formula (8): [Formula 8] The method of claim 1, Double spiro compound represented by the following formula (9): [Formula 9] The method of claim 1, Double spiro compound represented by the following formula (10): [Formula 10] The method of claim 1, Double spiro compound represented by the following formula (11): [Formula 11] The method of claim 1, Double spiro compound represented by the following formula (12): [Formula 12] The method of claim 1, Double spiro compound represented by the following formula (13): [Formula 13] The method of claim 1, Double spiro compound represented by the following formula (14): [Formula 14] The method of claim 1, Double spiro compound represented by the following formula (26): [Formula 26] The method of claim 1, Double spiro compound represented by the following formula (27): [Formula 27] The method of claim 1, Double spiro compound represented by the following formula (28): [Formula 28] The method of claim 1, Double spiro compound represented by the following formula (29): [Formula 29] The method of claim 1, Double spiro compound represented by the following formula (30): [Formula 30] The method of claim 1, Double spiro compound represented by the following formula (31): [Formula 31] The method of claim 1, Double spiro compound represented by the following Chemical Formula 32: [Formula 32] The method of claim 1, Double Spiro type compound represented by the following Chemical Formula 33: [Formula 33] The method of claim 1, Double spiro compound represented by the following formula (34): [Formula 34] delete delete delete The method of claim 1, Double spiro compound represented by the following formula (15): [Formula 15] The method of claim 1, Double spiro compound represented by the following formula (16): [Formula 16] The method of claim 1, Double spiro compound represented by the following formula (17): [Formula 17] The method of claim 1, Double spiro compound represented by the following formula (18): [Formula 18] The method of claim 1, Double spiro compound represented by the following formula (19): [Formula 19] The method of claim 1, Double spiro compound represented by the following formula (20): [Formula 20] The method of claim 1, Double spiro compound represented by the following formula (21): [Formula 21] The method of claim 1, Double spiro compound represented by the following formula (22): [Formula 22] The method of claim 1, Double spiro compound represented by the following formula (23): [Formula 23] The method of claim 1, Double spiro compound represented by the formula (24) [Formula 24] The method of claim 1, Double spiro compound represented by the formula (25) [Formula 25]