TWI588132B - Delayed fluorescence compound, and organic light emitting diode and display device using the same - Google Patents

Description

Delayed fluorescent compound, organic light emitting diode, and display using the organic light emitting diode Display device

The present invention relates to an organic light emitting diode (OLED), and more particularly to a delayed fluorescent compound having excellent luminous efficiency, an organic light emitting diode, and a display using the delayed fluorescent compound Device.

Due to the demand for large-sized display devices, flat-panel displays have been gradually developed as image display devices on the market. Among a wide variety of flat panel displays, organic light emitting diode display devices have developed quite rapidly.

In the organic light-emitting diode, the cathode is used as an electron injecting electrode, and the anode is injected as a hole into the electrode. When the electrons of the cathode and the hole of the anode are injected into the layer of the light-emitting material, the electron and the hole are combined. Excitons are generated so that they can emit light from the organic light emitting diode. A flexible substrate, such as a plastic substrate, can be used as a substrate material for an organic light-emitting diode, and the organic light-emitting diode has excellent characteristics such as voltage driving, power saving, and color purity.

The organic light-emitting diode includes a first electrode as an anode on a substrate and a second electrode as a cathode, the two electrodes facing each other with an organic light-emitting layer interposed therebetween.

In order to improve luminous efficiency, the organic light emitting layer may include a hole injection layer (HIL), a hole transport layer (HTL), an luminescent material layer (EML), and an electron transport layer (HTL) which are sequentially stacked on the first electrode. And an electron injection layer (EIL).

The hole is transmitted from the first electrode to the luminescent material layer via the hole injection layer and the hole transport layer, and the electron is transmitted from the second electrode to the electron transport layer through the electron injection layer and the electron transport layer. Light material layer.

The aforementioned electrons and holes are combined in the luminescent material layer to generate excitons which are generated from the excited state to the ground state to generate light.

The external quantum efficiency of the luminescent substance in the luminescent material layer can be expressed by the following equation: η _ext = η _int × Γ × Φ × η _out-coupling .

In the above equation, "η _int " represents the internal quantum efficiency, "r" represents the charge balance constant, "Φ" represents the emission quantum efficiency, and "η _out-coupling " represents the light extraction efficiency.

The charge balance constant "r" is the equilibrium constant between a hole and an electron when an exciton is generated. In general, the value of the charge balance constant is 1 when the hole-to-electron match is 1:1. The emission quantum efficiency "Φ" refers to the value of the luminescent material with respect to the effective luminous efficiency. In the primary illuminant-dopant system, the emission quantum efficiency varies with the fluorescent luminescence efficiency of the dopant.

The internal quantum efficiency "η _int " refers to the ratio of excitons that generate light to excitons generated by the combination of holes and electrons. In the fluorescent compound, the maximum internal quantum efficiency is 0.25. When a hole combines with electrons to generate excitons, the ratio of singlet excitons to triplet excitons according to the spin structure is 1:3. However, among the fluorescent compounds, only singlet excitons are used instead of triplet excitons for luminescence.

The light extraction efficiency "η _out-coupling " refers to the ratio of light emitted by the display device to light emitted from the luminescent material layer. When an isotropic compound is deposited by thermal evaporation to form a film, the luminescent material is diffusive. At this time, the light extraction efficiency of the display device can be assumed to be 0.2.

Therefore, the organic light-emitting diode containing a fluorescent compound as a light-emitting material has a maximum luminous efficiency of about 5%.

In order to overcome the disadvantage of poor luminous efficiency of fluorescent compounds, phosphorescent compounds capable of simultaneously emitting singlet excitons and triplet excitons have been developed for organic light emitting diodes.

Thus, red and green phosphorescent compounds having relatively high luminous efficiency have been introduced and developed. However, there are currently no blue phosphorescent compounds that meet the luminous efficiency and reliability requirements.

Accordingly, an embodiment of the present invention is directed to a delayed fluorescent compound, an organic light emitting diode, and a display device using the organic light emitting diode, which substantially obviate the limitations and disadvantages of the related prior art.

It is an object of an embodiment of the present invention to provide a delayed fluorescent compound having high luminous efficiency.

Another object of embodiments of the present invention is to provide an organic light emitting diode and a display device having improved luminous efficiency.

The other features and advantages of the invention will be set forth in part in the description in the appended claims. The objects and advantages of the invention may be realized and attain

In order to achieve the object and advantages of the embodiments of the present invention, an aspect of the present invention provides a delayed fluorescent compound represented by the following Chemical Formula 1 or Chemical Formula 2; a coated film on the organic light emitting diode. And a cover window on the cover film; [Chemical Formula 1] ;[Chemical Formula 2] Wherein each m and n are 1 or 0, and X ₁ is selected from the chemical formula 3; wherein, the L ₁ and L ₂ systems are each independently selected from the chemical formula 4, and the X ₂ and Y systems are respectively selected from the chemical formula 5 and the chemical formula 6 : [Chemical Formula 3] ;[Chemical Formula 4] ;[Chemical Formula 5] [Chemical Formula 6] Wherein R ₁ to R ₄ in the chemical formula 3 are each independently selected from a substituted or unsubstituted aromatic group; and R ₅ and R ₆ in the chemical formula 4 are each independently selected from hydrogen or a C ₁ to C ₁₀ alkane. And R ₇ in the chemical formula 5 is selected from hydrogen or phenyl.

Another aspect of the present invention provides an organic light emitting diode comprising: a first electrode; a second electrode facing the first electrode; and an organic light emitting layer attached to the first electrode Between the second electrode and the second electrode, the organic light-emitting layer comprises a delayed fluorescent compound represented by the following Chemical Formula 1 or Chemical Formula 2; a coated film on the organic light-emitting diode; and a coated film Covering window; [Chemical Formula 1] ;[Chemical formula Wherein, each m and n are 1 or 0, and X ₁ is selected from the chemical formula 3; wherein, the L ₁ and L ₂ systems are each independently selected from the chemical formula 4, and the X ₂ and Y systems are respectively selected from the chemical formula 5 and the chemical formula 6 :[Chemical Formula 3] ;[Chemical Formula 4] ;[Chemical Formula 5] ;[Chemical Formula 6] Wherein R ₁ to R ₄ in the chemical formula 3 are each independently selected from a substituted or unsubstituted aromatic group; and R ₅ and R ₆ in the chemical formula 4 are each independently selected from hydrogen or a C ₁ to C ₁₀ alkane. And R ₇ in the chemical formula 5 is selected from hydrogen or phenyl.

Another aspect of the present invention provides a display device including: a substrate; an organic light emitting diode on the substrate, the organic light emitting diode includes: a first electrode; a second electrode of the first electrode; and an organic light-emitting layer between the first electrode and the second electrode, the organic light-emitting layer comprising a delayed fluorescent compound represented by the following Chemical Formula 1 or Chemical Formula 2; a film coated on the organic light emitting diode; and a cover window attached to the cover film; [Chemical Formula 1] ;[Chemical Formula 2] Wherein, each m and n are 1 or 0, and X ₁ is selected from the chemical formula 3; wherein, the L ₁ and L ₂ systems are each independently selected from the chemical formula 4, and the X ₂ and Y systems are respectively selected from the chemical formula 5 and the chemical formula 6 :[Chemical Formula 3] ;[Chemical Formula 4] ;[Chemical Formula 5] [Chemical Formula 6] Wherein R ₁ to R ₄ in the chemical formula 3 are each independently selected from a substituted or unsubstituted aromatic group; and R ₅ and R ₆ in the chemical formula 4 are each independently selected from hydrogen or a C ₁ to C ₁₀ alkane. And R ₇ in the chemical formula 5 is selected from hydrogen or phenyl.

The above description and the following detailed description are merely illustrative of the embodiments of the invention.

110‧‧‧First electrode

120‧‧‧Organic light-emitting layer

121‧‧‧ hole injection layer

122‧‧‧ hole transport layer

123‧‧‧ luminescent material layer

124‧‧‧Electronic transport layer

125‧‧‧Electronic injection layer

130‧‧‧second electrode

E‧‧‧Organic Luminescent Diodes

S ₀ ‧‧‧ ground state

S ₁ ‧‧‧ singlet state

I ₁ ‧‧‧Intermediate state

T ₁ ‧‧‧ triplet

The accompanying drawings are intended to provide a further understanding of the invention

1 is a diagram showing the luminescence mechanism of the delayed fluorescent compound of the embodiment of the present invention; FIGS. 2A to 2F are diagrams showing the molecular structure of the compound having a triphenylamine electron-donating group; FIGS. 3A to 3F are respectively A molecular structure diagram of a compound having an electron donating group of diphenylpyridine; 4A to 4J are diagrams showing the properties of delayed fluorescent light of the delayed fluorescent compound of the embodiment of the present invention; and FIG. 5 is a schematic cross-sectional view showing the organic light emitting diode of the embodiment of the present invention.

The meanings of the terms used in this manual are as follows.

With regard to the identification of singular and plural, all singular terms include plural states unless otherwise stated. The terms "first", "second" and the like are used to distinguish only the elements, and the scope of the invention is not limited to the terms. The use of the terms "comprising", "comprising", and the like, does not exclude one or more features, integer values, steps, methods of operation, components, components, or combinations thereof. The term "at least one" includes a combination of one or more component items, for example: "at least one selected from the first item, the second item, and the third item", and includes not only selected from each of the first item, the second item, and The third item also includes all combinations of the first item, the second item and the third item which may be two or more. In addition, when an element is referred to as being "on" another element, it can be directly disposed on the top surface of the other element or a third element is interposed therebetween.

The related information will be presented in detail in the embodiments, and the embodiments will be described with reference to the drawings.

The delayed fluorescent compound of the present invention has the following chemical formula 1-1 or the chemical formula 1-2.

[Chemical Formula 1-2] Wherein, each m and n are 1 or 0.

That is, as shown in Chemical Formula 2-1, the delayed fluorescent compound has a structure in which an acridine electron-donating group is bonded by a linker L ₁ or to an electron-accepting group X ₁ . Alternatively, as shown in Chemical Formula 2-2, the structure of the delayed fluorescent compound may be constituted by directly bonding or linking to the electron-receiving group X _{1 of} the diphenylpyridine electron-donating group without passing through the linker.

Further, as shown in Chemical Formula 2-3, the structure of the delayed fluorescent compound may be the first electron supply group of the diphenylpyridine and the second electron supply group Y (which may be the same or different from the first electron supply group) ) is constituted by a linker L ₂ bonded or linked to an electron-receiving group X ₂ . In another aspect, as shown in Chemical Formula 2-4, the structure of the delayed fluorescent compound may also be from the first electron supply group of the diphenylpyridine and the second electron supply group Y (which may be the same or different from the first electron supply group). The group is directly bonded or linked to the electron accepting group X ₂ and is not permeable to the linker.

In Chemical Formulas 2-1 and 2-2, the electron accepting group X ₁ is selected from a substituted or unsubstituted triazine, a substituted or unsubstituted dibenzothiophene, a substituted or unsubstituted 4-nitrogen. 4-azabenzimidazole, or substituted or unsubstituted benzimidazole. For example, the electron accepting group X ₁ may be selected from the materials shown in Chemical Indication 3 below.

In Chemical Formula 3, R ₁ to R ₄ are each independently selected from hydrogen or a substituted or unsubstituted aromatic group. For example, each of R ₁ to R ₄ may be selected from hydrogen or an unsubstituted phenyl group.

In Chemical Formulas 1-1, 1-2, 2-1 and 2-3, L ₁ and L ₂ as a linker are substituted or unsubstituted toluene. For example, L ₁ and L ₂ may be materials shown in the following Chemical Formula 4.

In Chemical Formula 4, R ₅ and R ₆ are each independently selected from hydrogen or a C ₁ to C ₁₀ alkyl group. For example, each of R ₅ and R ₆ can be hydrogen or methyl.

In the formulae 1-2, 2-3 and 2-4, the electron accepting group X ₂ is selected from substituted or unsubstituted phenyltriazine, dibenzothiophenesulfone, diphenyl. Diphenylsulfone, quinoxaline, thieno pyrazine, or a derivative thereof. For example, the electron accepting group X ₂ may be selected from the materials shown in Chemical Formula 5 below.

In Chemical Formula 5, R ₇ is selected from hydrogen or phenyl.

In the formulae 1-2, 2-3 and 2-4, the second electron supply group Y is selected from materials which can be injected into a hole, for example, carbazole, triphenylamine, diphenyl. Acridine or a derivative thereof. That is, the second electron-donating group Y is selected from a substituted or unsubstituted triphenylamine, a substituted or unsubstituted diphenylamine, or a substituted or unsubstituted diphenylpyridine. For example, The two electron supply group Y may be selected from the materials shown in Chemical Formula 6 below.

Since the delayed fluorescent compound includes an electron supply group, an electron accepting group, and/or no other electron supply group, charge transport is easily generated between molecules, thereby improving luminous efficiency. Furthermore, the dipole generation from the first and second electron donating groups to the electron accepting group also increases the dipole moment of the molecule.

On the other hand, in the delayed fluorescent compound of the present invention, triplet excitons are also used for light emission, and thus the luminous efficiency of the delayed fluorescent compound can be improved.

Furthermore, since the hexagonal structure of diphenylpyridine is used as the electron supply group, the steric hindrance between the electron supply group and the electron accepting group will increase, and the two sides between the electron supply group and the electron accepting group The angle will also increase. Therefore, the conjugation between the electron-donating group and the electron-receiving group will be limited, so that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are easily separated, and the luminous efficiency of the delayed fluorescent compound is made. Further gains.

In the delayed fluorescent compound of the present invention, the overlap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital is reduced due to the bonding or linkage between the electron-donating group and the electron-receiving group in the molecule. Therefore, an electric field activated complex is generated, and the luminous efficiency of the delayed fluorescent compound is improved.

Since there is a linker between the electron supply group and the electron accepting group, the gap or distance between the two increases, and the overlap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital reduces the singlet energy and The energy gap between the triplet states (ΔE _ST ).

In addition, since the linker causes steric hindrance, the problem of red offset generated when the light-emitting layer containing the retardation fluorescent compound emits light is reduced or reduced. That is, containing the delayed fluorescence of the present invention The luminescent layer of the compound is capable of producing deep blue luminescence.

Please refer to Fig. 1, which is a schematic diagram showing the luminescence mechanism of the delayed fluorescent compound of the present invention. In the delayed fluorescent compound of the present invention, both singlet excitons and triplet excitons are used for luminescence, thereby improving luminous efficiency.

That is, the triplet excitons are activated by the electric field, and the triplet excitons and the singlet excitons are transitioned to the intermediate state "I ₁ ", and then transition to the ground state "S ₀ " to emit light. In other words, both the singlet "S ₁ " and the triplet "T ₁ " are transitioned to the intermediate state "I ₁ " (S ₁ -> I ₁ <-T ₁ ), while the single is in the intermediate state "I ₁ " Both heavy excitons and triplet excitons are used for luminescence, thus improving luminous efficiency. A compound having the aforementioned luminescence mechanism may be referred to as a field activated delayed fluorescence (FADF).

In some related fluorescent compounds, since the highest occupied molecular orbital and the lowest unoccupied molecular orbital are dispersed throughout the molecule, it is impossible to convert the highest occupied molecular orbital with the lowest unoccupied molecular orbital. ).

However, in the electric field-activated delayed fluorescent compound, since the overlap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital in the molecule is relatively small, the interaction between the two is also small. Therefore, a change in the state of an electron spin does not affect other electrons, and thus, a new charge transfer band that does not conform to the selection rule is generated.

Further, since the electron supply group and the electron-receiving group are in separate spaces in the molecule, a dipole moment is generated in a polarized state. In the polarization state, the dipole moment, the interaction between the highest occupied molecular orbital and the lowest unoccupied molecular orbital is further reduced, so that the illuminating mechanism does not conform to the selection rule. Thus, the activation delay field fluorescent compound, can be generated by the triplet "T _1" and the singlet state "S _1" to the intermediate state "I _1" transition, so that a triplet exciton can be used for light emission.

When the organic light-emitting diode is driven, an intersystem crossing of a 25% singlet "S ₁ " exciton and a 75% triplet "T ₁ " exciton transition to an intermediate state "I ₁ " is generated, and The singlet or triplet excitons in the intermediate state "I ₁ " are then transitioned to the ground state to emit light. Therefore, the electric field activation retardation fluorescent compound (FADF) theoretically has a luminous efficiency of 100%.

For example, the delayed fluorescent compound of the present invention may be one of the compounds represented by Chemical Formula 7.

As described above, the delayed luminescent compound of the present invention comprises a diphenylpyridine electron supply. The group is added to increase the steric hindrance between the electron donating group and the electron accepting group, and the dihedral angle between the electron donating group and the electron accepting group.

2A to 2F are diagrams showing the molecular structure of a compound having a triphenylamine electron-donating group, and FIGS. 3A to 3F are diagrams showing a molecular structure of a compound having a diphenylpyridine electron-donating group.

Referring to FIGS. 2A to 2F, in the compound containing triphenylamine as an electron-donating group, the dihedral angle between the electron-donating group and the electron-accepting group (or linker) is about 44 degrees.

On the other hand, referring to Figures 3A to 3F, in a compound containing diphenylpyridine as an electron-donating group, the dihedral angle between the electron-donating group and the electron-accepting group (or linker) is about 90. degree.

That is, when diphenylpyridine is used as the electron supply group, the dihedral angle between the electron supply group of the diphenylpyridine and the electron accepting group is increased, so that the electron supply group and the electron accepting group (or linker) The conjugation between them is limited. Therefore, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the compound containing the diphenylpyridine electron-donating group are easily separated from the lowest unoccupied molecular orbital (LUMO), and the luminescence is further enhanced as compared with the compound containing the triphenylamine electron-donating group. effectiveness.

synthesis

1. Synthesis of Compound 1

(1) Compound a

In a nitrogen purge system, 14.6 mmol of 2,8-dibromodibenzothiophene was mixed with an acetic acid solvent and stirred. Then, 64.8 mmole of hydrogen peroxide was added, and the mixture was stirred at room temperature for about 30 minutes, and the mixed solution was refluxed and stirred for 12 hours. the above. After the reaction was completed, 50 ml of distilled water was added thereto, stirred, and filtered. After filtering the mixed solution, the solid is mixed with an excess of hydrogen peroxide and stirred for 30 to 60 minutes. After the solid was washed with distilled water, filtered and dried, compound a was obtained as a white solid (yield 90%).

(2) Compound b

In a nitrogen purge system, 46.9 mmol of N-phenylanthraniliic acid was mixed with a methanol solvent and stirred. The mixed solution was then further stirred at 0 ° C for 10 minutes, and 21.2 mmol of thionyl chloride was slowly added dropwise thereto. Thereafter, the mixed solution was stirred at 90 ° C for 12 hours or more. After the reaction was completed, the solvent was removed, and the mixed solution was extracted with distilled water and ethyl acetate. The magnesium is removed from the extracted organic layer using magnesium sulfide, and the solvent is removed. This product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound b (yield 81%) as a dark yellow liquid.

(3) Compound c

In a nitrogen purge system, 38.1 mmol of compound b was mixed with tetrahydrofuran and stirred. Thereafter, 4.6-fold equivalents of methyl magnesium bromide was slowly added dropwise, and the reaction was stirred at room temperature for 12 hours or more. After the reaction was completed, distilled water was slowly added, and the solution was extracted with ethyl acetate. Removal of the extracted organic layer using magnesium sulfate Remove water and remove solvent. This product was further subjected to wet purification using hexanes and ethyl acetate in a column chromatography to obtain Compound C (yield: 87%) as a dark yellow liquid.

(4) Compound d

In a nitrogen purge system, 33.1 mmol of compound c was added to a 160 ml excess phosphoric acid solution and stirred at room temperature. This solution was further stirred for more than 16 hours, and 200 to 250 ml of distilled water was slowly added during the period. The solution was then stirred for 0.5 to 1 hour and the precipitated solid was filtered. The filtered solid was then extracted with an aqueous solution of sodium hydroxide and a solvent of dichloromethane. The water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed to obtain a compound d (yield 69%) as a white solid.

(5) Compound e

In a nitrogen purge system, compound a was dissolved in a toluene solvent and 0.9 times equivalent of phenylboronic acid was added. Further, after 4 times equivalent of potassium carbonate was dissolved in distilled water, it was added to the above mixed solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalents of palladium. After the mixed solution was refluxed, it was stirred at 80 °C. After completion of the reaction, the mixed solution was extracted with ethyl acetate and distilled water, and water was removed from the extracted organic layer using magnesium sulfate. The remaining organic solvent was removed, and the resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain a solid compound e (yield 68%).

(6) Compound 1

In a nitrogen purge system, compound e, 1.1 equivalents of compound d, 0.019 equivalents of Pd(OAc) ₂ , 0.046 equivalents (50 wt%) of P(t-Bu) _3, and 1.9 equivalents of tert-butanol Sodium tert-butoxide is added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 1 (yield 55%).

2. Synthesis of Compound 2

(1) Compound f

In a nitrogen purifying system, 23.9 mmol of compound d, 35.8 mmol of 1,4-dibromobenzene, 2 mol% of palladium (II) acetate, and 5 mol% of phosphoric acid were used. Tri-tert-butylphosphate and 2.03 equivalents of sodium t-butoxide were added to the toluene solvent and stirred. After the mixed solution was refluxed, it was stirred for 12 hours. After the reaction was completed, the solution was extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product produced is further utilized by hexane and ethyl acetate in the column The product was obtained as a dark yellow liquid (yield 81%) by wet purification in a chromatograph.

(2) Compound g

In a nitrogen purge system, compound f, 1.2 equivalents of bis(pinacolate) diboron, [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride dichloride Methane ([1,1-bis(diphenylphosphineo)ferrocene]palladium(II)dichloride dichloromethane), 1,1-bis(diphenylphosphino)ferrocene and potassium acetate Stir in a 1:1 1,4-dioxane/toluene solution in a dark-proof Erlenmeyer flask and stir. After the bubbles disappeared, the solution was stirred at 120 ° C for 17 hours. After the reaction was completed, the solution was cooled to room temperature, and then the solvent was removed. After the resulting product was washed with toluene and purified, Compound g (yield 90%) was obtained.

(3) Compound 2

In a nitrogen purge system, compound e was dissolved in a toluene solvent and 1.2 times equivalent of compound g was added. Further, 8.8 equivalents of potassium carbonate was dissolved in distilled water and added to the aforementioned solution. Thereafter, tetrahydrofuran was added, and 0.1 equivalent of palladium was further added. This mixed solution is returned After the flow, stirring was carried out at 80 °C. After the reaction is completed, the mixed solution is extracted with aqueous sodium hydroxide solution and toluene, and water is removed from the extracted organic layer by using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further subjected to hexane in a tube. After wet purification and recrystallization in a column chromatography, Compound 2 (yield 56%) was obtained.

3. Synthesis of Compound 3

(1) Compound h

In a nitrogen purge system, 4-phenylbromosulfone was dissolved in a toluene solvent and 0.9 times equivalent of phenylboronic acid was added. Further, 4 times equivalent of potassium carbonate was dissolved in distilled water and added to the above solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalents of palladium. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with distilled water and ethyl acetate, and water is removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further utilized with hexane and ethyl acetate. The ester was subjected to wet purification in a column chromatography to obtain a solid compound h (yield 75%).

(2) Compound 3

In a nitrogen purge system, compound h, 1.1 equivalents of compound d, 0.019 equivalents of Pd(OAc) ₂ , 0.046 equivalents (50 wt%) of P(t-Bu) _3, and 1.9 equivalents of tert-butanol Sodium tert-butoxide is added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 3 (yield: 65%).

4. Synthesis of Compound 4

In a nitrogen purge system, compound h was dissolved in a toluene solvent, and 1.2 times equivalent of compound g was added. Further, 8.8 equivalents of potassium carbonate was dissolved in distilled water and added to the aforementioned solution. Thereafter, tetrahydrofuran was added, and 0.1 equivalent of palladium was further added. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with aqueous sodium hydroxide solution and toluene, and water is removed from the extracted organic layer by using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further subjected to hexane in a tube. After wet purification and recrystallization in a column chromatography, Compound 4 (yield 60%) was obtained.

5. Synthesis of Compound 5

[Reaction formula 5]

In a nitrogen purge system, 5 mol% of Pd(dba) ₂ as a catalyst and 4 mol% of P(t-Bu) _{3 were} added to a toluene solvent and stirred for 15 minutes. Thereafter, 33.8 mol of 2-chloro-4,6-diphenyl-1,3,5-triazine and 33.8 mol were added. Compound d and 60.6 mol of NaOt-Bu were stirred at 90 ° C for 5 hours. After the reaction was completed, the mixed solution was filtered with diatomaceous earth, and the solvent was removed. The filtered solid was further subjected to wet purification in a column chromatography using hexane and dichloromethane, and recrystallized from hexane to obtain Compound 5 (yield: 59%).

6. Synthesis of Compound 6

In a nitrogen purge system, 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.1 equivalents of compound g, 5 equivalents of sodium carbonate, and ammonium chloride are added to a 1:1 ratio. The toluene/distilled water solvent was added and stirred. The solution was stirred for 30 minutes under a nitrogen atmosphere, and then 0.05 equivalent of tetrakis(triphenylphosphine) Pd(0) was added. After the solution was stirred for 10 minutes, stirring was continued at 100 ° C for 16 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with dichloromethane. After that, the water is removed from the extracted organic layer by using magnesium sulfate, and then removed. The remaining organic solvent. The product thus obtained was further subjected to wet purification in a column chromatography using dichloromethane, and recrystallized from chloroform to obtain a solid compound 6 (yield 70%).

7. Synthesis of Compound 7

(1) Compound i

In a nitrogen purge system, 0.1 times equivalent of copper iodide and 0.2 times equivalent of 1,10-phenanthroline were added to dimethylformamide (DMF). In the solvent, then 4-azabenzimidazole, 1.2-fold equivalent of 1-bromo-4-iodobenzene, and 2-fold equivalent of cesium carbonate (cesium) Carbonate). After refluxing the solution, it was stirred at 110 ° C for 16 hours. After the reaction was completed, the DMF solvent was removed, and the product was extracted with dichloromethane. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using hexane and ethyl acetate in a column chromatography, and recrystallized from dichloromethane to give compound i (yield 78%).

(2) Compound 7

In a nitrogen purge system, compound i, 1.1 equivalents of compound d, 0.019 equivalents of Pd(OAc) ₂ , 0.046 equivalents (50 wt%) of P(t-Bu) _3, and 1.9 equivalents of tert-butanol Sodium tert-butoxide is added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using a hexane and ethyl acetate in a column chromatography to obtain Compound 7 (yield 60%).

8. Synthesis of Compound 8

(1) Compound j

In a nitrogen purge system, 0.1 times equivalent of copper iodide and 0.2 times equivalent of 1,10-phenanthroline were added to dimethylformamide (DMF). In the solvent, then 4-azabenzimidazole, 1.3 times equivalent of 1-bromo-3,5-dimethyl-4-iodobenzene (1-bromo-3,5-dimethyl) -4-iodobenzene) and 2 equivalents of cesium carbonate. After refluxing the solution, it was stirred at 110 ° C for 16 hours. After the reaction was completed, the DMF solvent was removed, and the product was extracted with dichloromethane. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification by hexane and ethyl acetate in a column chromatography, and recrystallized from dichloromethane to give compound j (yield 60%).

(2) Compound 8

[Reaction formula 8-2]

In a nitrogen purge system, compound j, 1.1 equivalents of compound d, 0.019 equivalents of Pd(OAc) ₂ , 0.046 equivalents (50 wt%) of P(t-Bu) _3, and 1.9 equivalents of tert-butanol Sodium tert-butoxide is added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 8 (yield 50%).

9. Synthesis of Compound 9

(1) Compound k

In a nitrogen purge system, 0.1 times equivalent of copper iodide and 0.2 times equivalent of 1,10-phenanthroline were added to dimethylformamide (DMF). In the solvent, then 4-azabenzimidazole, 1.2-fold equivalent of 1-bromo-4-iodobenzene, and 2-fold equivalent of cesium carbonate (cesium) Carbonate). After refluxing the solution, it was stirred at 110 ° C for 16 hours. After the reaction was completed, the DMF solvent was removed, and the product was extracted with dichloromethane. After The water was removed from the extracted organic layer with magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography, and recrystallized from dichloromethane to give compound k (yield: 80%).

(2) Compound 9

In a nitrogen purge system, compound k, 1.1 equivalents of compound d, 0.019 equivalents of Pd(OAc) ₂ , 0.046 equivalents (50 wt%) of P(t-Bu) _3, and 1.9 equivalents of tert-butanol Sodium tert-butoxide is added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 9 (yield 62%).

10. Synthesis of Compound 10

(1) Compound l

In a nitrogen purge system, 0.1 times equivalent of copper iodide And 0.2 times equivalent of 1,10-phenanthroline is added to the solvent of dimethylformamide (DMF), followed by 4-azabenzimidazole. 1.3 equivalents of 1-bromo-3,5-dimethyl-4-iodobenzene and 2 equivalents of cesium carbonate. After refluxing the solution, it was stirred at 110 ° C for 16 hours. After the reaction was completed, the DMF solvent was removed, and the product was extracted with dichloromethane. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification by hexane and ethyl acetate in a column chromatography, and recrystallized from dichloromethane to give Compound 1 (yield: 58%).

(2) Compound 10

In a nitrogen purge system, compound l, 1.1 equivalents of compound d, 0.019 equivalents of Pd(OAc) ₂ , 0.046 equivalents (50 wt%) of P(t-Bu) _3, and 1.9 equivalents of tert-butanol Sodium tert-butoxide is added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using a hexane and ethyl acetate column chromatography to give Compound 10 (yield 46%).

11. Synthesis of Compound 11

(1) Compound a

[Reaction formula 11-1]

In a nitrogen purge system, 46.9 mmol of N-phenylanthraniliic acid was added to a methanol solvent and stirred. The mixed solution was then further stirred at 0 ° C for 10 minutes, and 21.2 mmol of thionyl chloride was slowly added dropwise thereto. Thereafter, the mixed solution was stirred at 90 ° C for 12 hours or more. After the reaction was completed, the solvent was removed, and the mixed solution was extracted with distilled water and ethyl acetate. The magnesium is removed from the extracted organic layer using magnesium sulfide, and the solvent is removed. This product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound a (yield 81%) as a dark yellow liquid.

(2) Compound b

In a nitrogen purge system, 38.1 mmol of compound a was mixed with tetrahydrofuran and stirred. Thereafter, 4.6-fold equivalents of methyl magnesium bromide was slowly added dropwise, and the reaction was stirred at room temperature for 12 hours or more. After the reaction was completed, distilled water was slowly added dropwise, and the solution was extracted with ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. This product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound b (yield: 87%) as a yellow liquid.

(3) Compound c

[Reaction formula 11-3]

In a nitrogen purge system, 33.1 mmol of compound b was added to a 160 ml excess phosphoric acid solution and stirred at room temperature. This solution was further stirred for more than 16 hours, and 200 to 250 ml of distilled water was slowly added during the period. The solution was then stirred for 0.5 to 1 hour and the precipitated solid was filtered. The filtered solid was then extracted with an aqueous solution of sodium hydroxide and a solvent of dichloromethane. The water was removed from the extracted organic layer using magnesium sulfate, and the organic solvent was removed to obtain a compound c (yield 69%) as a white solid.

(4) Compound d

In a nitrogen purification system, 23.9 mmol of compound c, 35.8 mmol of 1,4-dibromobenzene, 2 mol% of palladium (II) acetate, and 5 mol% of phosphoric acid were used. Tri-tert-butylphosphate and 2.03 equivalents of sodium t-butoxide were added to the toluene solvent and stirred. After the mixed solution was refluxed, it was stirred for 12 hours. After the reaction was completed, the solution was extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain compound d (yield 81%).

(5) Compound e

[Reaction formula 11-5]

In a nitrogen purge system, compound d, 1.2 equivalents of bis(pinacolate) diboron, [1,1-bis(diphenylphosphino)ferrocene]palladium dichloride dichloride Methane ([1,1-bis(diphenylphosphineo)ferrocene]palladium(II)dichloride dichloromethane), 1,1-bis(diphenylphosphino)ferrocene and potassium acetate Stir in a 1:1 1,4-dioxane/toluene solution in a dark-proof Erlenmeyer flask and stir. After the bubbles disappeared, the solution was stirred at 120 ° C for 17 hours. After the reaction was completed, the solution was cooled to room temperature, and then the solvent was removed. After the resulting product was washed with toluene and purified, Compound e (yield 90%) was obtained.

(6) Compound f

In a nitrogen purge system, 14.6 mmol of 2,8-dibromodibenzothiophene was mixed with an acetic acid solvent and stirred. Thereafter, 64.8 mmole of hydrogen peroxide was added, and the mixture was stirred at room temperature for about 30 minutes, and the mixed solution was refluxed and stirred for 12 hours or more. After the reaction was completed, 50 ml of distilled water was added thereto, stirred, and filtered. After filtering the mixed solution, the solid is mixed with an excess of hydrogen peroxide and stirred for 30 to 60 minutes. After the solid was washed with distilled water, filtered and dried, compound f (yield 90%) was obtained as a white solid.

(7) Compound 11

In a nitrogen purge system, compound f was dissolved in a toluene solvent and 2.4 times equivalent of compound e was added. Further, 8.8 equivalents of potassium carbonate was dissolved in distilled water and added to the aforementioned solution. Thereafter, tetrahydrofuran was added, and 0.1 equivalent of palladium was further added. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with aqueous sodium hydroxide solution and toluene, and water is removed from the extracted organic layer by using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further subjected to hexane in a tube. After wet purification and recrystallization in a column chromatography, Compound 11 (yield 85%) was obtained.

12. Synthesis of Compound 12

(1) Compound g

In a nitrogen purifying system, 29.9 mmol of carbazole, 44.9 mmol of 1,4-dibromobenzene, 2 mol% of palladium (II) acetate, and 5 mol% of Phosphoric acid tri-tert-butylphosphate and 2.03 equivalents of sodium t-butoxide were added to the toluene solvent and stirred. After the mixed solution was refluxed, it was stirred for 12 hours. After the reaction was completed, the solution was extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product is further utilized The compound g (yield 80%) was obtained by wet-purifying hexane and ethyl acetate in a column chromatography.

(2) Compound h

In a nitrogen purge system, compound g was dissolved in tetrahydrofuran and stirred. Then, 26.9 mmol of n-butyl-lithium was slowly added at -78 ° C, and the reaction was stirred for 1 hour. Under continuous low temperature, 21.6 mmol of tri-ethylborate was added, and then the mixed solution was stirred at room temperature, and the reaction was completed after stirring for 12 hours. Distilled water was slowly added, and a mixed solution of 8:2 distilled water/hydrochloric acid was further added to a pH of 2. This solution was extracted with distilled water and ethyl acetate. The water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. This product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain compound h (yield: 87%).

(3) Compound i

In a nitrogen purge system, compound f is dissolved in toluene solvent and then added to 0.9 A compound equivalent of h. Further, 4 times equivalent of potassium carbonate was dissolved in distilled water and added to the above solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalents of palladium. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with distilled water and ethyl acetate, and water is removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further utilized with ethyl acetate and The solid was subjected to wet purification in a column chromatography to obtain a solid compound i (yield: 65%).

(4) Compound 12

In a nitrogen purge system, compound i was dissolved in a toluene solvent and 1.2 equivalents of compound e was added. Further, 8.8 equivalents of potassium carbonate was dissolved in distilled water and added to the aforementioned solution. Thereafter, tetrahydrofuran was added, and 0.1 equivalent of palladium was further added. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with aqueous sodium hydroxide solution and toluene, and water is removed from the extracted organic layer by using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further subjected to hexane in a tube. After wet purification and recrystallization in a column chromatography, Compound 12 (yield 75%) was obtained.

13. Synthesis of Compound 13

[Reaction formula 13]

In a nitrogen purge system, 4-bromophenylsulfone was dissolved in a toluene solvent and 2.4 equivalents of compound e was added. Further, 8.8 equivalents of potassium carbonate was dissolved in distilled water and added to the aforementioned solution. Thereafter, tetrahydrofuran was added, and 0.1 equivalent of palladium was further added. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with aqueous sodium hydroxide solution and toluene, and water is removed from the extracted organic layer by using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further subjected to hexane in a tube. After wet purification and recrystallization in a column chromatography, Compound 13 (yield 78%) was obtained.

14. Synthesis of Compound 14

(1) Compound j

In a nitrogen purge system, 4-bromophenylsulfone was dissolved in a toluene solvent and 0.9 times equivalent of compound h was added. Further, 4 times equivalent of potassium carbonate was dissolved in distilled water and added to the above solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalent of palladium. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with distilled water and ethyl acetate, and water is removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further utilized with acetic acid. The ester and hexane were subjected to wet purification in a column chromatography to obtain a solid compound j (yield 60).

(2) Compound 14

In a nitrogen purge system, compound j was dissolved in a toluene solvent and 1.2 equivalents of compound e was added. Further, 8.8 equivalents of potassium carbonate was dissolved in distilled water and added to the aforementioned solution. Thereafter, tetrahydrofuran was added, and 0.1 equivalent of palladium was further added. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with aqueous sodium hydroxide solution and toluene, and water is removed from the extracted organic layer by using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further subjected to hexane in a tube. After wet purification and recrystallization in a column chromatography, Compound 14 (yield 55%) was obtained.

15. Synthesis of Compound 15

(1) Compound k

In a light-proof conical flask of a nitrogen purifying system, 0.9 times equivalent at -78 ° C After bromobenzene is dissolved in tetrahydrofuran, n-butyl-lithium is slowly added dropwise. Further, 2,4,6-trichloro-1,3,5-triazine (2,4,6-trichloro-1,3,5-triazine) was dissolved in tetrahydrofuran, and then dropped into the foregoing by a cannula under a nitrogen atmosphere. The solution was stirred for 8 hours. After completion of the reaction, the product thus obtained was further purified to obtain compound k (yield 45%).

(2) Compound 15

In a nitrogen purge system, compound k, 2.1 equivalents of compound e, 5 equivalents of sodium carbonate, ammonium chloride were added to a 1:1 toluene/distilled water solvent and stirred. After stirring for 30 minutes under a nitrogen atmosphere, 0.05 equivalent of tetrakis(triphenylphosphine) Pd(0) was added. After the solution was stirred for 10 minutes, stirring was continued at 100 ° C for 16 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with dichloromethane. Thereafter, water is removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent is removed. The resulting product was further subjected to wet purification in a column chromatography using dichloromethane and hexane, and recrystallized from chloroform and acetonitrile to obtain compound 15 (yield 75%). .

16. Synthesis of Compound 16

(1) Compound l

[Reaction formula 16-1]

In a nitrogen purge system, compound k, 0.9-fold equivalent of compound h and 0.6-fold equivalent of sodium carbonate were placed in a solvent of 1:1:0.7 toluene/di-decane/distilled water and stirred. Thereafter, 0.3 equivalents of tetrakis(triphenylphosphine)Pd(0), Pd(PPh ₃ ) ₄ ) was further added and stirred for 16 hours. After the reaction was completed, the solution was cooled to room temperature. The organic layer was washed with distilled water in a silica gel and filtered. Then, the solvent and distilled water were removed, and the resulting product was subjected to wet purification in a column chromatography apparatus and dried to obtain Compound 1 (yield 80%).

(2) Compound 16

In a nitrogen purge system, Compound 1, 1.05 equivalents of Compound e, 5 equivalents of sodium carbonate, and ammonium chloride were added to a 1:1 toluene/distilled water solvent and stirred. After stirring for 30 minutes under a nitrogen atmosphere, 0.05 equivalent of tetrakis(triphenylphosphine) Pd(0) was added. After the solution was stirred for 10 minutes, stirring was continued at 100 ° C for 16 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with dichloromethane and distilled water. Thereafter, water is removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent is removed. The resulting product is further utilized in the column layer of dichloromethane and hexane. After wet purification in a crystallizer and recrystallization from chloroform and acetonitrile, Compound 16 (yield 60%) was obtained.

17. Synthesis of Compound 17

(1) Compound m

In a nitrogen purge system, 3 g of 2,3-hydroxyquinoxaline (2,3-hydroquinoxaline) was placed in a PBr ₅ solvent and stirred at 160 ° C for 4 hours. After the reaction was completed, the solution was cooled to 0 ° C and stirred for 30 minutes. This mixed solution was further extracted with dichloromethane and distilled water, and washed with 1N sodium hydroxide. Thereafter, the water was removed by using magnesium sulfate, and the resulting product was concentrated to obtain a compound m (yield: 96%).

(2) Compound 17

Compound m, 3 equivalents of compound e, 0.1 equivalents of Pd ₂ (dba) ₃ , 0.1 equivalents of tricyclohexylphosphine (tri-cyclohexylphosphine) and 1.35 M potassium phosphate (K ₃ PO ₄ ) aqueous solution are added. Mix in two decane solvents. This mixed solution was refluxed and stirred for 48 hours in a nitrogen purge system. After the reaction was completed, the solution was cooled to room temperature and extracted with dichloromethane and distilled water. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification and recrystallization using dichloromethane and hexane in a column chromatography to obtain Compound 17 (yield 36%).

18. Synthesis of Compound 18

(1) Compound n

In a nitrogen purge system, compound m was dissolved in a toluene solvent and 0.9 times equivalent of compound h was added. Further, 4 times equivalent of potassium carbonate was dissolved in distilled water and added to the above solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalents of palladium. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with distilled water and ethyl acetate, and water is removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further utilized with ethyl acetate and After the alkane was subjected to wet purification in a column chromatography and recrystallized, a solid compound n (yield 55%) was obtained.

(2) Compound 18

In a nitrogen purge system, compound n was dissolved in a toluene solvent and 1.2 equivalents of compound h was added. Further, 8.8 equivalents of potassium carbonate was dissolved in distilled water and added to the aforementioned solution. Thereafter, tetrahydrofuran was added, and 0.1 equivalent of palladium was further added. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction is completed, the mixed solution is extracted with aqueous sodium hydroxide solution and toluene, and water is removed from the extracted organic layer by using magnesium sulfate, and the remaining organic solvent is removed, and the resulting product is further subjected to hexane in a tube. After wet purification and recrystallization in a column chromatography, Compound 18 (yield 45%) was obtained.

19. Synthesis of Compound 19

(1) Compound a

In a nitrogen purge system, 14.6 mmol of 2,8-dibromodibenzothiophene was mixed with an acetic acid solvent and stirred. Thereafter, 64.8 mmol of hydrogen peroxide was added, and the mixture was stirred at room temperature for about 30 minutes, and the mixed solution was refluxed and stirred for 12 hours or more. After the reaction was completed, 50 ml of distilled water was added thereto, stirred, and filtered. After filtering the mixed solution, the solid is mixed with an excess of hydrogen peroxide and stirred for 30 to 60 minutes. After the solid was washed with distilled water, filtered and dried, compound a was obtained as a white solid (yield 90%).

(2) Compound b

46.9 mmol of N-aniline benzoic acid in a nitrogen purge system (N-phenylanthraniliic acid) was mixed with a methanol solvent and stirred. The mixed solution was then further stirred at 0 ° C for 10 minutes, and 21.2 mmol of thionyl chloride was slowly added dropwise thereto. Thereafter, the mixed solution was stirred at 90 ° C for 12 hours or more. After the reaction was completed, the solvent was removed, and the mixed solution was extracted with distilled water and ethyl acetate. The magnesium is removed from the extracted organic layer using magnesium sulfide, and the solvent is removed. The product thus obtained was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain compound b (yield 81%) as a dark yellow liquid.

(3) Compound c

In a nitrogen purge system, 38.1 mmol of compound b was mixed with tetrahydrofuran and stirred. Thereafter, 4.6-fold equivalents of methyl magnesium bromide was slowly added dropwise to the solution, and the solution was stirred at room temperature for 12 hours or more. After the reaction was completed, distilled water was slowly added, and the solution was extracted with ethyl acetate. The water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. This product was further subjected to wet purification using hexanes and ethyl acetate in a column chromatography to obtain Compound C (yield: 87%) as a dark yellow liquid.

(4) Compound d

In a nitrogen purge system, 33.1 mmol of compound c was added to a 160 ml excess phosphoric acid solution and stirred at room temperature. This solution was further stirred for more than 16 hours, and 200 to 250 ml of distilled water was slowly added during the period. The solution was then stirred for another 0.5 to 1 hour, and the precipitated solid was filtered. The filtered solid was then extracted with an aqueous solution of sodium hydroxide and a solvent of dichloromethane. The water was removed from the extracted organic layer using magnesium sulfate, and the organic solvent was removed to obtain a compound d (yield 69%) as a white solid.

(5) Compound 19

In a nitrogen purge system, 0.3 mol of compound d, 0.15 mol of compound a, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to give Compound 19 (yield 81%).

20. Synthesis of Compound 20

In a nitrogen purge system, 0.3 mol of compound d, 0.15 mol of 4-bromophenylsulfone, 6.11 mmol of Pd(OAc) ₂ , and 15.28 mmol (50 wt%) of P(t-Bu) _{3 were used.} And 0.61 mol of sodium tert-butoxide was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 20 (yield: 80%).

21. Synthesis of Compound 21

(1) Compound e

In a light-proof conical flask of a nitrogen purifying system, 0.9 times equivalent of bromobenzene was dissolved in tetrahydrofuran at -78 ° C, and then n-butyl-lithium was slowly added dropwise. ). Further, 2,4,6-trichloro-1,3,5-triazine (2,4,6-trichloro-1,3,5-triazine) was dissolved in tetrahydrofuran, and then dropped into the foregoing by a cannula under a nitrogen atmosphere. The solution was stirred for 8 hours. After completion of the reaction, the product thus obtained was further purified to obtain Compound e (yield 45%).

(2) Compound 21

In a nitrogen purge system, 5 mol% of Pd(dba) ₂ as a catalyst and 4 mol% of P(t-Bu) _{3 were} added to a toluene solvent and stirred for 15 minutes. Thereafter, 33.8 mol of the compound 2, 16.9 mol of the compound d and 60.6 mol of NaOt-Bu were further added, and the mixture was stirred at 90 ° C for 5 hours. After the reaction was completed, the mixed solution was filtered with diatomaceous earth, and the solvent was removed. The filtered solid was further subjected to wet purification in a column chromatography using hexane and dichloromethane, and recrystallized from hexane to obtain Compound 21 (yield: 59%).

22. Synthesis of Compound 22

In a nitrogen purge system, 0.3 mol of compound d, 0.15 mol of 5,8-dibromo-quinoxaline, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) P(t-Bu) ₃ and 0.61 mol of sodium tert-butoxide were added to a toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 22 (yield: 79%).

23. Synthesis of Compound 23

(1) Compound f

[Reaction formula 23-1]

In a nitrogen purge system, 5.52 mmol of 3,4-diaminothiophene dihydrochloride was slowly added to 60 ml of 5% sodium carbonate and 6.1 ml of glyoxal in 5 minutes. In the solution. Thereafter, 15 mol of a 40% diluted glyoxal solution was further added. The mixed solution was stirred at room temperature for 3 hours, and extracted rapidly with ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed without heating. The solid was washed with diethyl ether. The resulting product was further subjected to wet purification in a column chromatography using dichloromethane and hexane to obtain compound f (yield 70%).

(2) Compound g

In a nitrogen purge system, 14.7 mmol of compound f was added to a 1:1 chloroform/acetic acid solvent and stirred. The solution was then cooled to 0 ° C and 32.3 mmol of N-Bromsuccinimid (NBS) was added. The mixed solution was then stirred at room temperature for 12 hours. After the completion of the reaction, distilled water equivalent to the reaction solvent was added to the mixed solution, and the solution was extracted with chloroform. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed without heating. The solid was washed with diethyl ether. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain compound g (yield: 75%).

(3) Compound 23

[Reaction formula 23-3]

In a nitrogen purge system, 0.3 mol of compound d, 0.15 mol of compound g, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 23 (yield 70%).

24. Synthesis of Compound 24

(1) Compound h

In a nitrogen purge system, carbazole is dissolved in a 1,4-dioxane solvent, followed by copper iodide and potassium phosphate. Further, 1.1 times equivalent of compound a and trans-1,2-diaminocyclohexane were added. After the mixed solution was refluxed, it was stirred at 110 ° C for 24 hours. After completion of the reaction, the solution was cooled to room temperature, extracted with distilled water and ethyl acetate, and water was removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent was removed, and the resulting product was further developed. The solid compound h was obtained by wet purification using hexane and ethyl acetate in a column chromatography (yield 58%)

(2) Compound 24

In a nitrogen purge system, 0.33 mol of compound d, 0.33 mol of compound h, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 24 (yield 55%).

25. Synthesis of Compound 25

(1) Compound h

In a nitrogen purge system, carbazole is dissolved in a 1,4-dioxane solvent, followed by copper iodide and potassium phosphate. Further, 1.1 equivalents of 4-bromophenylsulfone and trans-1,2-diaminocyclohexane were added. After the mixed solution was refluxed, it was stirred at 110 ° C for 24 hours. After completion of the reaction, the solution was cooled to room temperature, extracted with ethyl acetate and distilled water, and water was removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent was removed, and the resulting product was further developed. Ethyl acetate and hexane in a column chromatography By wet purification, a solid compound i (yield 60%) was obtained.

(2) Compound 25

In a nitrogen purge system, 0.33 mol of compound d, 0.33 mol of compound i, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using a hexane and ethyl acetate in a column chromatography to obtain Compound 25 (yield: 65%).

26. Synthesis of Compound 26

(1) Compound j

In a nitrogen purge system, compound a was dissolved in a toluene solvent, and 1.1 equivalents of 4-(diphenylamino)phenylboronic acid was added. Further, after 4 times equivalent of potassium carbonate was dissolved in distilled water, it was added to the above mixed solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalents of palladium. This solution is refluxed at 80 ° C Stir. After completion of the reaction, the mixed solution was extracted with ethyl acetate and distilled water, and water was removed from the extracted organic layer using magnesium sulfate. The remaining organic solvent was removed, and the resulting product was further subjected to wet purification using ethyl acetate and hexanes on a column chromatography to obtain compound j (yield: 56%).

(2) Compound 26

In a nitrogen purge system, 0.33 mol of compound d, 0.33 mol of compound j, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using a hexane and ethyl acetate in a column chromatography to obtain Compound 26 (yield 50%).

27. Synthesis of Compound 27

(1) Compound k

In a nitrogen purge system, 4-bromophenylsulfone was dissolved in a toluene solvent, and 1.1 equivalents of 4-(diphenylamino)phenylboronic acid was added. Further, after dissolving 4.4 equivalents of potassium carbonate in distilled water, it was added to the above mixed solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalents of palladium. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction was completed, the mixed solution was extracted with ethyl acetate, and water was removed from the extracted organic layer using magnesium sulfate. The remaining organic solvent was removed, and the resulting product was further subjected to wet purification in a column chromatography using dichloromethane and hexane to obtain compound k (yield 55%).

(2) Compound 27

In a nitrogen purge system, 0.33 mol of compound d, 0.33 mol of compound k, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 27 (yield 45%).

28. Synthesis of Compound 28

(1) Compound l

[Reaction formula 28-1]

In a nitrogen purge system, carbazole is dissolved in a 1,4-dioxane solvent, followed by copper iodide and potassium phosphate. Further, 1.1 equivalents of 5,8-dibromoquinoxaline and trans-1,2-diaminocyclohexane were added. After the mixed solution was refluxed, it was stirred at 110 ° C for 24 hours. After completion of the reaction, the solution was cooled to room temperature, extracted with ethyl acetate and distilled water, and water was removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent was removed, and the resulting product was further developed. The compound 1 was obtained by wet purification using ethyl acetate and hexane in a column chromatography (yield 48%).

(2) Compound 28

In a nitrogen purge system, 0.33 mol of compound d, 0.33 mol of compound 1, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using a hexane and ethyl acetate in a column chromatography to obtain Compound 28 (yield 50%).

29. Synthesis of Compound 29

(1) Compound m

In a nitrogen purification system, 5,8-dibromoquinoxalinee was dissolved in a toluene solvent, and 1.1 equivalents of 4-(diphenylamine)phenylboronic acid (4-(diphenylamino) was added. )phenylboronic acid). Further, after dissolving 4.4 equivalents of potassium carbonate in distilled water, it was added to the above mixed solution. Thereafter, tetrahydrofuran was added, followed by 0.05 equivalents of palladium. After the mixed solution was refluxed, it was stirred at 80 °C. After the reaction was completed, the mixed solution was extracted with ethyl acetate, and water was removed from the extracted organic layer using magnesium sulfate. After removing the remaining organic solvent, the resulting product was further subjected to wet purification in a column chromatography using dichloromethane and hexane to obtain compound m (yield: 43%).

(2) Compound 29

In a nitrogen purge system, 0.33 mol of compound d, 0.33 mol of compound m, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The resulting product was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 29 (yield 50%).

30. Synthesis of Compound 30

(1) Compound n

In a nitrogen purge system, carbazole is dissolved in a 1,4-dioxane solvent, followed by copper iodide and potassium phosphate. Further, 1.1 times equivalent of compound g and trans-1,2-diaminocyclohexane were added. After the mixed solution was refluxed, it was stirred at 110 ° C for 24 hours. After completion of the reaction, the solution was cooled to room temperature, extracted with ethyl acetate and distilled water, and water was removed from the extracted organic layer using magnesium sulfate, and the remaining organic solvent was removed, and the resulting product was further developed. The solid-state compound n (yield 45%) was obtained by wet purification using ethyl acetate and hexane in a column chromatography.

(2) Compound 30

In a nitrogen purge system, 0.33 mol of compound d, 0.33 mol of compound n, 6.11 mmol of Pd(OAc) ₂ , 15.28 mmol (50 wt%) of P(t-Bu) ₃ and 0.61 mol of sodium t-butoxide ( Sodium tert-butoxide) was added to the toluene solvent and stirred. This solution was refluxed and stirred at 120 ° C for 12 hours. After the reaction was completed, the solution was cooled to room temperature and extracted with distilled water and ethyl acetate. Thereafter, water was removed from the extracted organic layer using magnesium sulfate, and the solvent was removed. The product thus obtained was further subjected to wet purification using hexane and ethyl acetate in a column chromatography to obtain Compound 30 (yield 49%).

The mass spectral data of the aforementioned compounds 1 to 30 are shown in Table 1.

Among the above compounds, the luminescent properties of the compounds 3, 6, 7, 9, 11, 15, 16, 23, 27 and 29 were measured and the results are shown in Table 2 and shown in Figures 4A to 4J (Quantarus tau) Apparatus of Hamamatsu Co., Ltd. under anaerobic conditions).

As shown in Table 2 and Figures 4A to 4J, the delayed fluorescent compound (Compounds 3, 6, 7, 9, 11, 15, 16, 23, 27) of the present invention has hundreds to tens of thousands of nanoseconds ( Ns) delayed luminescence characteristics.

As described above, after the delayed fluorescent compound of the present invention is activated by an electric field, both the singlet state "S ₁ " and the triplet state "T ₁ " are transitioned to the intermediate state "I ₁ ". Therefore, both singlet excitons and triplet excitons can be utilized for luminescence.

The electric field activation retardation fluorescent compound (FADF) is a single molecule having an electron supply group, an electron accepting group, and/or no other electron supply group, and thus is liable to cause charge transfer. Electric Field Activation Delays Fluorescent Compounds Under special circumstances, the charge is separated from the electron donating group to the electron accepting group.

The electric field activation delays the fluorescent compound to be activated by external factors. It was confirmed by comparing the difference between the absorption peak and the emission peak of the compound solution.

In the above formula, "△υ" refers to the stock-shift value, and "υabs" and "υfl" refer to the maximum absorption peak and the maximum emission peak, respectively. "h" refers to Planck's constant, "c" refers to the speed of light, "a" refers to the onsager cavity radius, and "△μ" refers to the excited state and the ground state. The dipole moment difference (Δμ=μe-μg).

"△f" means the orientational polarizability of the solvent, which may be a function of the solvent dielectric constant (ε) as a function of the solvent refractive index (n).

Since the intensity of the dipole moment in the excited state is determined by the peripheral polarity (for example, the polarity of the solvent), the electric field activation retardation fluorescent compound can be confirmed by the difference between the absorption peak and the emission peak of the compound solution.

The orientation polarizability (?f) of the mixed solvent can be obtained by calculation of each pure solvent and its molar fraction. When a pattern in which Δf is linearly related to Δυ using the aforementioned Lippert-Mataga equation, the compound may provide FADF luminescence.

That is, when the FADF complex is stabilized due to the orientation polarization of the solvent, the emission peak will shift by a long wavelength depending on the angle of the stabilization. Therefore, when the compound provides FADF luminescence, Δf and Δυ are in a straight line on the graph. That is, when Δf is linear with Δυ, the compound provides FADF luminescence.

In the delayed fluorescent compound of the present invention, 25% of singlet excitons and 75% of triplet excitons are transitioned to an intermediate state by external forces (for example, an electric field generated when an organic light-emitting diode is driven) Transition). The excitons in the intermediate state are then transitioned to the ground state to emit light. That is, in the delayed fluorescent compound, both singlet excitons and triplet excitons are used for luminescence, thereby improving luminous efficiency.

Organic light-emitting diode

An indium tin oxide layer was deposited on a substrate and etched to form an anode (3 mm * 3 mm). The substrate is placed in a vacuum space, and a hole injection layer (500Å, N, N'-bis(naphthyl-1-) is sequentially formed on the anode at a bottom pressure of about 10 ^-6 to 10 ^-7 Torr. N,N'-diphenyl-benzidine), NPB), a hole transport layer (100Å, N, N'-Dicarbazolyl-3, 5-benzene, mCP), a layer of luminescent material (350Å, main illuminant: two [2- ((Oxo)diphenylphosphino)phenyl]ether) with 6% dopant, an electron transport layer (300Å, 1, 3) , 5-tris(phenyl-2-benzimidazole)-benzene, an electron injecting layer (lithium fluoride), and a cathode (aluminum) .

(1) Comparative Example 1 (control)

The control compound in Chemical Formula 8 is used as a doping for forming an organic light-emitting diode Things.

(2) Embodiment 1

Compound 3 serves as a dopant for forming an organic light-emitting diode.

(3) Embodiment 2

Compound 6 serves as a dopant for forming an organic light-emitting diode.

(4) Embodiment 3

Compound 7 serves as a dopant for forming an organic light-emitting diode.

(5) Embodiment 4

Compound 9 serves as a dopant for forming an organic light-emitting diode.

(6) Embodiment 5

Compound 11 serves as a dopant for forming an organic light-emitting diode.

(7) Embodiment 6

Compound 13 serves as a dopant for forming an organic light-emitting diode.

(8) Example 7

Compound 15 serves as a dopant for forming an organic light-emitting diode.

(9) Embodiment 8

Compound 16 serves as a dopant for forming an organic light-emitting diode.

(10) Embodiment 9

Compound 17 is used as a dopant for forming an organic light-emitting diode.

(11) Embodiment 10

Compound 19 serves as a dopant for forming an organic light-emitting diode.

(12) Embodiment 11

Compound 20 serves as a dopant for forming an organic light-emitting diode.

(13) Example 12

Compound 21 serves as a dopant for forming an organic light-emitting diode.

(14) Example 13

Compound 22 serves as a dopant for forming an organic light-emitting diode.

(15) Example 14

Compound 23 serves as a dopant for forming an organic light-emitting diode.

(16) Example 15

Compound 24 serves as a dopant for forming an organic light-emitting diode.

(17) Embodiment 16

Compound 30 serves as a dopant for forming an organic light-emitting diode.

As shown in Table 3, the organic light-emitting diodes of the compounds of the present invention (Examples 1 to 6) were improved in both driving voltage and luminous efficiency.

Fig. 5 is a schematic cross-sectional view showing an organic light emitting diode according to the present invention.

As shown in FIG. 5, the organic light-emitting diode E is formed on a substrate (not shown), and the organic light-emitting diode E includes a first electrode 110 as an anode and a second electrode as a cathode. 130, and an organic light emitting layer 120 between the first two.

Although not shown in the drawings, a cover film comprising at least one inorganic layer and at least one organic layer covers the organic light-emitting diode E, and a cover window may be formed on the cover film to manufacture a display device. The substrate, the cover film and the cover window may be flexible, and a flexible display device may be provided.

The first electrode 110 is made of a material having a relatively high work function, and the second electrode 120 is made of a material having a relatively low work function. For example, the first electrode 110 may be made of a material of indium tin oxide (ITO), and the second electrode 130 may be made of a material of aluminum or aluminum alloy (AlNd). The organic light emitting layer 120 may include red, green, and blue light emitting types.

The organic light emitting layer 120 may have a single layer structure. In addition, to improve the luminous efficiency, the organic light emitting layer 120 may include a hole injection layer 121, a hole transport layer 122, a light emitting material layer 123, an electron transport layer 124, and an electron injection layer 125 which are sequentially stacked on the first electrode 110.

At least one selected from the group consisting of the hole injection layer 121, the hole transport layer 122, the luminescent material layer 123, the electron transport layer 124, and the electron injection layer 125 includes retardation fluorescence represented by Chemical Formula 1-1 or Chemical Formula 1-2 Compound.

For example, the luminescent material layer 123 may include a delayed fluorescent compound represented by Chemical Formula 1-1 or Chemical Formula 1-2. The delayed fluorescent compound acts as a dopant, and the luminescent material layer 123 can further include a primary illuminant to emit blue light. In this case, the dopant accounts for about 1 to 30% by weight of the main illuminant.

The HOMO (HOMO _Host ) of the main illuminator is different from the HOMO (HOMO _Dopant ) of the dopant, or the difference between the LUMO (LUMO _Host ) of the main illuminant and the LUMO (LUMO _Dopant ) of the dopant is less than 0.5. eV[(HOMO _Host -HOMO _Dopant ) 0.5eV or (LUMO _Hos -LUMO _Dopant ) 0.5eV]. In this case, the charge transfer efficiency from the main illuminant to the dopant is improved.

The main illuminant satisfying the above conditions may be selected from the materials as shown in Chemical Formula 9. For example, the following sequence is: [2-((dioxyphosphino)phenyl)ether oxide (DPEPO)], 2,8-II (2,8-bis(diphenylphosphoryl)dibenzothiophene(PPT)], 2,8-bis(9H-triphenylamine-9-yl)dibenzothiophene [2,8 -di(9H-carbazol-9-yl)dibenzothiophene(DCzDBT)], m-bis(carbazol-9-yl)biphenyl(m-CBP)], Diphenyl-4-triphenylsilylphenyl-phosphine oxide (TPSO1) and 9-(9-phenyl-9H-triphenyl-6-yl)-9H-triphenyl [9-(9-phenyl-9H-carbazol-6-yl)-9H-carbazole (CCP)].

The triplet energy of the dopant is smaller than the triplet energy of the main illuminant, and the difference between the singlet energy of the dopant and the triplet energy of the main illuminator is less than 0.3 eV (ΔE _ST 0.3eV). The smaller the ΔE _{ST is} , the higher the luminous efficiency is. In the delayed fluorescent compound of the present invention, even if the singlet state energy of the dopant differs from the triplet energy of the main illuminant by ΔE _{ST of} about 0.3 eV, the value is quite large, but the singlet state "S ₁ Excitons and triplet "T ₁ " excitons can still transition to the intermediate state "I ₁ ".

On the other hand, the delayed fluorescent compound of the present invention may also function as a main illuminant in the luminescent material layer 123, and the luminescent material layer 123 may further contain a dopant to emit blue light. In this case, the dopant accounts for about 1 to 30% by weight of the main illuminant. Due to the lack of development of a blue light illuminator having excellent characteristics, the delayed luminescent compound of the present invention can be used as a main illuminant to increase the degree of freedom of the main illuminant. In this case, the triplet energy of the dopant may be less than the triplet energy of the delayed phosphorescent host illuminator of the present invention.

The luminescent material layer 123 can include a first dopant, a primary illuminant, and a second dopant of the delayed fluorescent compound of the present invention. The sum of the weight percentages of the first and second dopants may be about 1 to 30 to emit blue light. In this case, the luminous efficiency and the color purity can be further improved.

In this case, the triplet energy of the first dopant (eg, the delayed fluorescent compound of the present invention) may be less than the triplet energy of the primary illuminant and greater than the triplet energy of the second dopant. In addition, the difference between the singlet state energy of the first dopant and the triplet energy of the first dopant is less than 0.3 eV (ΔE _ST 0.3eV). The smaller the ΔE _{ST is} , the higher the luminous efficiency is. In the delayed fluorescent compound of the present invention, even if the singlet state energy of the dopant differs from the triplet energy of the dopant by ΔE _{ST of} about 0.3 eV, the value is quite large, but the singlet state "S ₁ Excitons and triplet "T ₁ " excitons can still transition to the intermediate state "I ₁ ".

As described above, since the delayed fluorescent compound of the present invention includes an electron supply group, an electron accepting group, and/or no other electron supply group, the acridine electron supply group and the electron accepting group A large steric hindrance is formed, thereby improving the luminous efficiency. In addition, the first and second electron-donating groups are generated for the dipole of the electron-receiving group such that the dipole moment of the molecule also increases. Therefore, the luminous efficiency is improved. In addition, in the delayed fluorescent compound of the present invention, triplet excitons are also used for luminescence, thereby improving the luminous efficiency of the late fluorescent compound.

Due to the presence of the linker, the gap or distance between the electron donating group and the electron accepting group increases, which reduces the overlap between HOMO and LUMO, and also reduces the energy gap between the triplet energy and the singlet energy (ΔE _ST ). . In addition, since the linker causes steric hindrance, the problem of red offset generated when the light-emitting layer containing the retardation fluorescent compound emits light is reduced or reduced.

Therefore, the organic light-emitting diode using or containing the delayed fluorescent compound of the present invention and the display device have the advantage of high luminous efficiency.

Any person skilled in the art will be able to make some modifications and refinements without departing from the spirit and scope of the invention, and the scope of the invention is defined by the scope of the appended claims.

The present invention claims the following priority of Korean Patent Application: Application No.: 10-2014-0156946, Application Date: December 12, 2014; Application No.: 10-2014-0169004, Application Date: November 28, 2014; Application No.: 10-2014-0169077, application date: November 28, 2014; application number: 10-2015-0141568, application date: October 8, 2015; application number: 10-2015-0141569, application date: October 8, 2015; and application number: 10-2015-0141570, filing date: October 8, 2015, the entire contents of which is incorporated herein by reference.

Claims (16)

A delayed fluorescent compound represented by the following Chemical Formula 1 or Chemical Formula 2: Wherein, each m and n are 1 or 0, and X ₁ is selected from the chemical formula 3; wherein, the L ₁ and L ₂ systems are each independently selected from the chemical formula 4, and the X ₂ and Y systems are respectively selected from the chemical formula 5 and the chemical formula 6: [Chemical Formula 4] Wherein R ₁ to R ₄ in the chemical formula 3 are each independently selected from a substituted or unsubstituted aromatic group; and R ₅ and R ₆ in the chemical formula 4 are each independently selected from hydrogen or a C ₁ to C ₁₀ alkyl group. And R ₇ in the chemical formula 5 is selected from hydrogen or phenyl; and wherein X ₁ in the chemical formula ₁ is When m=1. The delayed fluorescent compound according to claim 1, wherein a difference between a singlet state energy of the delayed fluorescent compound and a triplet energy of the delayed fluorescent compound is less than 0.3 eV. An organic light emitting diode comprising: a first electrode; a second electrode facing the first electrode; and an organic light emitting layer between the first electrode and the second electrode, the organic light emitting layer The retardation fluorescent compound represented by the following Chemical Formula 1 or Chemical Formula 2 is included: Wherein, each m and n are 1 or 0, and X ₁ is selected from the chemical formula 3; wherein, the L ₁ and L ₂ systems are each independently selected from the chemical formula 4, and the X ₂ and Y systems are respectively selected from the chemical formula 5 and the chemical formula 6: Wherein R ₁ to R ₄ in the chemical formula 3 are each independently selected from a substituted or unsubstituted aromatic group; and R ₅ and R ₆ in the chemical formula 4 are each independently selected from hydrogen or a C ₁ to C ₁₀ alkyl group. And R ₇ in the chemical formula 5 is selected from hydrogen or phenyl; and wherein X ₁ in the chemical formula ₁ is When m=1. The organic light-emitting diode according to claim 3, wherein a difference between a singlet state energy of the delayed fluorescent compound and a triplet energy of the delayed fluorescent compound is less than 0.3 eV. The organic light-emitting diode according to claim 3, wherein the organic light-emitting layer further comprises a main light-emitting body, and the delayed fluorescent compound is used as a dopant. The organic light-emitting diode according to claim 5, wherein the highest occupied molecular orbital (HOMO) of the main illuminant is different from the highest occupied molecular orbit of the dopant, or the main illuminating The difference between the lowest unoccupied molecular orbital (LUMO) of the body and the lowest unoccupied molecular orbital of the dopant is less than 0.5 eV. The organic light-emitting diode according to claim 3, wherein the organic light-emitting layer further comprises a dopant, and the delayed fluorescent compound is a main light-emitting body. The organic light emitting diode according to claim 3, wherein the organic light emitting layer further comprises a main light emitting body and a first dopant, and the delayed fluorescent compound is used as a second dopant. And wherein the triplet energy of the second dopant is less than the triplet energy of the main emitter, but greater than the triplet energy of the first dopant. The organic light-emitting diode of claim 3, wherein the organic light-emitting layer comprises a hole injection layer, a hole transport layer, a light-emitting material layer, an electron transport layer, and an electron injection layer, and Wherein at least one selected from the group consisting of the hole injection layer, the hole transport layer, the luminescent material layer, the electron transport layer and the electron injection layer comprises the delayed fluorescent compound. A display device comprising: a substrate; an organic light emitting diode on the substrate, the organic light emitting diode comprising: a first electrode; a second electrode facing the first electrode; An organic light-emitting layer between the first electrode and the second electrode, the organic light-emitting layer comprising a delayed fluorescent compound represented by the following Chemical Formula 1 or Chemical Formula 2; a coated film attached to the organic light-emitting diode And a cover window attached to the cover film; Wherein, each m and n are 1 or 0, and X ₁ is selected from the chemical formula 3; wherein, the L ₁ and L ₂ systems are each independently selected from the chemical formula 4, and the X ₂ and Y systems are respectively selected from the chemical formula 5 and the chemical formula 6: Wherein R ₁ to R ₄ in the chemical formula 3 are each independently selected from a substituted or unsubstituted aromatic group; and R ₅ and R ₆ in the chemical formula 4 are each independently selected from hydrogen or a C ₁ to C ₁₀ alkyl group. And R ₇ in the chemical formula 5 is selected from hydrogen or phenyl; and wherein X ₁ in the chemical formula ₁ is When m=1. The display device of claim 10, wherein the difference between the singlet state energy of the delayed fluorescent compound and the triplet energy of the delayed fluorescent compound is less than 0.3 eV. The display device of claim 10, wherein the organic light-emitting layer further comprises a main light-emitting body, and the delayed fluorescent compound is used as a dopant. The display device of claim 12, wherein the highest occupied molecular orbital (HOMO) of the primary illuminant is different from the highest occupied molecular orbital of the dopant, or the lowest of the primary illuminant The difference between the unoccupied molecular orbital (LUMO) and the lowest unoccupied molecular orbital of the dopant is less than 0.5 eV. The display device of claim 10, wherein the organic light-emitting layer further comprises a dopant, and the delayed fluorescent compound is a primary light-emitting body. The display device of claim 10, wherein the organic light-emitting layer further comprises a main light-emitting body and a first dopant, and the delayed fluorescent compound is used as a second dopant, and wherein The triplet energy of the second dopant is less than the triplet energy of the main emitter, but greater than the triplet energy of the first dopant. The display device of claim 10, wherein the organic light-emitting layer comprises a hole injection layer, a hole transport layer, a light-emitting material layer, an electron transport layer and an electron injection layer, and wherein At least one of the group consisting of the hole injection layer, the hole transport layer, the luminescent material layer, the electron transport layer, and the electron injection layer includes the delayed fluorescent compound.