KR20170131730A - Noble Compound Exhibiting Thermally Activated Delayed Fluorescence and Organic Light-Emitting device Using the Same - Google Patents

Abstract

The present invention relates to a novel compound which due to having little difference between a singlet energy state and a triplet energy state, exhibits a thermally activated delayed fluorescence by reverse intersystem crossing when heat is applied, that generates the singlet energy state from the triplet energy state; and to an organic light-emitting device which applies the same to a dopant of an organic light-emitting layer. Specifically, the present invention relates to a compound represented by chemical formula 1; and to an organic light-emitting device which applies the same to a dopant of an organic light-emitting layer, wherein in the chemical formula 1, R_1 and R_2 may be identical or different from each other, and are a pyridoindole group, a phenyl group, a carbazole group, a 9,9-dimethyl-9,10-dihydroacridine group, a 10H-phenothiazine group, or 10H-phenoxazine group, and R_3 is a methyl or phenyl group.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a novel compound exhibiting delayed fluorescence and an organic light-

The present invention relates to a novel compound exhibiting a thermally-activated delayed fluorescence in which a transition from a triplet energy level to a single-energy level takes place when thermal energy is applied due to a difference between a single-term energy level and a triplet energy level, To an organic light emitting diode.

Recently, the proportion of flat display devices with high power efficiency and small space occupancy is gradually increasing due to the development and size of portable electronic communication equipment. Liquid crystal displays (LCDs) are the most popular method currently used, in which the liquid crystal is energized to pass the light from the backlight through a color filter to obtain a three-color display. On the other hand, organic light emitting diodes (OLEDs) are self-luminous elements having excellent viewing angles and contrast ratios, are lightweight and thin, can be used for boards having bending properties, and can realize transparent and flexible displays Has attracted attention as a next generation display device. Further, as the application range of organic EL devices has been expanded, many researches have been made.

The organic light emitting device has a structure in which an organic light emitting layer containing an organic light emitting compound is laminated between an anode and a cathode. When a voltage is applied to the organic light emitting device, holes are injected from the anode and electrons from the cathode are injected into the organic light emitting layer, respectively. The holes and electrons reaching the organic light emitting layer recombine to form excitons of the organic light emitting compound. The excitons emit light when returned to the ground state, and the organic light emitting element is an element using light emitted at this time.

The organic luminescent layer can be roughly classified into a host material and a dopant material exhibiting luminescent characteristics, and is distinguished from a fluorescent material and a phosphorescent material according to a luminescent mechanism. The excited state of the electrons in the compound is 1: 3 ratio of singlet to triplet, and triplet state is generated about 3 times more. Therefore, in a fluorescent material, only about 25% of the excitons formed in the organic light emitting layer emit light, whereas 75% of the triplet is lost to heat, so that the internal quantum efficiency of fluorescence becomes 25% of the maximum limit. Practical fluorescence type organic light emitting devices have been developed for long life, and are used for cellular phones and televisions, but the actual luminous efficiency is only 10% or less.

On the other hand, since phosphorescence emits light by triplet exciton, the maximum internal quantum efficiency of phosphorescence is 75%, which is higher than that of fluorescence. Moreover, if the inter-phase transition from singlet state to triplet state occurs efficiently, the theoretical limit of internal quantum efficiency can reach theoretically 100%. However, although the red phosphorescent material has been put to practical use, the blue phosphorescent material and the blue phosphorescent material are shorter in life time than the commercially available red and green phosphorescent materials and blue fluorescent material, and their commercialization is delayed due to insufficient color purity and luminous efficiency.

As an alternative to blue phosphors with low lifespan, studies on the emission of thermally activated delayed fluorescence (TADF) have been actively conducted. This is due to the fact that the difference between the singlet energy level and the triplet energy level (ΔST) is small and the inter-phase transition from triplet state to singlet state occurs due to thermal energy. The use of a substance showing TADF (TADF substance) makes it possible to raise the internal quantum efficiency to 100% theoretically even in a fluorescent light emitting material.

International Publication WO-A-2010-134350 discloses an organic light emitting device using a fluoranthene derivative as a dopant as a TADF material. However, the device exhibits a maximum light emitting efficiency at a low current such as 0.01 mA / cm ² , There is a problem that the roll-off phenomenon occurs at a practical high current of about 10 mA / cm < ² > to lower the luminous efficiency. Therefore, in order to utilize the delayed fluorescent light by the TADF material, it is necessary to develop a new material capable of increasing the luminous efficiency at a high current.

In Japanese Patent Application Laid-Open No. 10-2015-0016242, it has been reported that non-cyclized benzene sulfone compounds are useful as a light emitting material for organic light emitting devices. However, these compounds have excellent external light emitting efficiency of 19.5% . As to the use of a compound having a cyclized benzenesulfone skeleton as a light emitting material of an organic light emitting device, the utility of a compound having a cyclized benzenesulfone skeleton has been confirmed for a very small number of compounds, and systematic research has not yet been conducted.

International Publication No. 2010-134350 Published Japanese Patent Application No. 10-2015-0016242

An object of the present invention is to provide a novel organic luminescent compound which is excellent in thermal stability and exhibits thermal activation delay fluorescence due to a small difference between singlet energy level and triplet energy level.

Another object of the present invention is to provide an organic light emitting device having a high luminous efficiency without causing a roll-off phenomenon even at a high current using the novel compound.

In order to accomplish the above object, the present invention relates to a compound represented by the following general formula (1).

[화학식 1]

[Chemical Formula 1]

Here, R ₁ and R ₂ may be the same or different from each other, and may be a pyridone ring, a phenyl group, a carbazole group, a 9,9-dimethyl-9,10-dihydraacridine group, a 10H- And R < ₃ > is methyl or phenyl group.

In addition, the pyridoyl group, the phenyl group, or the carbazole group of R ₁ and R ₂ may have an electron-exciting group of an alkyl group, a carbazole group, a phenyl group or a diphenyl amino group as a substituent.

Conventional phosphorescent materials having a high exciton generation efficiency require expensive iridium complex compounds, so that the compounds can be produced without using expensive catalysts, and thus the economical efficiency is greatly improved. Further, the compounds showed stability to heat due to the stable cyclic structure, and they showed that the luminescence efficiency was excellent due to the retardation fluorescence due to thermal activation due to the inverse phase transition due to the small difference between the singlet energy level and the triplet energy level. These properties indicate that the compounds of the present invention have properties suitable as light emitting materials for organic light emitting devices.

Accordingly, the present invention provides an organic light emitting device comprising an anode, a cathode, and an organic light emitting layer interposed between the anode and the cathode, wherein the organic light emitting layer contains the compound of the present invention as an organic light emitting material. In particular, the organic light-emitting layer further includes a phosphor as a host, and the compound of the present invention is preferably used as a dopant. It is preferable that at least one of the excited triplet energies and excited triplet energies of the phosphorescent material has a higher value than the excited triplet energies of the dopant.

The organic light emitting device of the present invention has been described as a basic structure of the anode / organic light emitting layer / cathode. However, in order to increase the efficiency of the organic light emitting device, at least one layer selected from a hole injection layer, a hole transport layer, a hole blocking layer, Can be added. The material forming each of the layers is not particularly limited, and a person skilled in the art will be able to easily select a compound to be used for each layer.

The compounds of the present invention as described above has value because it does not require the use of expensive catalyst synthesis is possible can be manufactured economically and thermally very since it has a stable structure and 1 ~ 10 mA / cm ² degree practical high roll at a current-off phenomenon Can be minimized.

In addition, since the compound of the present invention exhibits retardation fluorescence with a small difference between singlet energy and triplet energy level, it is possible to provide an organic light emitting device having excellent external quantum efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing the structure of a material used in the production of an organic light-emitting device according to an embodiment of the present invention. FIG.
2 is a graph showing the driving voltage of a compound according to an embodiment of the present invention.
3 is a graph showing external quantum efficiency according to wavelength of a compound according to an embodiment of the present invention.
4 is a graph showing the maximum emission wavelength of a compound according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are merely examples for explaining the content and scope of the technical idea of the present invention, and thus the technical scope of the present invention is not limited or changed. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

[Example]

Example 1: Synthesis Example

The compounds of the present invention were prepared from the precursor VII by a coupling reaction with a compound having a structure of R < ₁ > and R < ₂ > according to the following generalized scheme. The following reagents were purchased from Aldrich-Sigma, TCI, Almadis chemical. In the following Synthesis Examples, the synthesis method is described in detail by taking the representative materials as an example. However, other derivatives having the structure of Formula (1) can also be produced by reacting a precursor corresponding to the structure of R ₁ and R ₂ of each compound And can be easily synthesized according to the same or modified method. It is therefore to be understood that the compounds of the present invention are not limited to the specific examples of the compounds listed below.

Pre-synthesis: Preparation of precursor compounds VIIa and VIIb

2,7-Dibromo-9,9-dimethyl-9H-thioxanthene-10,10-dioxide (VII) as a precursor for preparing the compound of formula (1) was prepared by the following reaction formula.

1) Synthesis of methyl 2- (phenylthio) benzoate (III)

To 400 ml of xylene was added 44 g (0.2 mol) of compound I, 28.6 g (0.2 mol) of compound II, , 2.85 g (7.5 mol%) of CuI and 1.7 g of 1,2-diaminocyclohexane were added, and the mixture was stirred under reflux for 18 hours. The reaction solution was cooled to room temperature, filtered, and then concentrated under reduced pressure. The concentrated residue was purified by column chromatography to obtain 43 g of Compound (III) (yield: 85.7%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 7.95 (d, 1H), 7.59 (t, 2H), 7.41 (d, 3H), 7.22 (t, 2H), 7.13 (t, 1H), 3.95 (s, 3H)

2) Synthesis of 2- (2- (phenylthio) phenyl) propan-2-ol (IVa)

24.4 g (0.1 mol) of Compound III was added to 250 ml of tetrahydrofuran, and the mixture was cooled to -15 ° C. Then, 83.4 ml of 3M methylmagnesium chloride was slowly added thereto. After 1 hour, the mixture was stirred at 0 ° C for 3 hours and at room temperature for 3 hours. 250 ml of a saturated ammonium chloride solution was slowly added, and 200 ml of ethyl acetate was added to separate an organic layer. The organic layer was concentrated under reduced pressure and purified by column chromatography to obtain 16.5 g of Compound IVa (Yield: 67.6%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 7.70 (d, 1H), 7.45 ~ 7.41 (t, 2H), 7.25 (t, 2H), 7.12 ~ 7.19 (d, 4H), 1.65 (s, 6H)

3) Synthesis of diphenyl (2- (phenylthio) phenyl) methanol (IVb)

23.4 g of the compound (IVb) (yield: 63.6%) was obtained in the same manner as in 2), except that 33.5 ml of 2M phenylmagnesium chloride in place of 3 M methylmagnesium chloride was used.

Mass: M ^{+ 1} = 369

4) Synthesis of 9,9-dimethyl-9H-thioxanthene (Va)

16.5 g (67.52 mmol) of the compound IVa was added to 50 g of polyphosphoric acid and reacted at 85 to 90 ° C for 2 hours. 250 ml of purified water and 200 ml of ethyl acetate were added to the reaction mixture, which was stirred for 1 hour, and then the organic layer was separated.

The organic layer was successively washed with saturated aqueous sodium chloride (250 ml) and saturated brine (250 ml), and then the organic layer was concentrated under reduced pressure. The concentrated residue was purified by column chromatography to obtain 13.6 g of Compound Va (yield: 89%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 7.51 (d, 1H), 7.44 (d, 1H), 7.30 (t, 4H), 7.15 (d, 2H), 1.68 (s, 6H)

5) Synthesis of 9,9-diphenyl-9H-thioxanthene (Vb)

19.2 g of the compound (Vb) was obtained (yield: 81.3%) by the same method as in 4), except that 24.85 g of the compound IVb was used in place of the compound IVa.

Mass: M ^{+ 1} = 351

6) Synthesis of 2,7-dibromo-9,9-dimethyl-9H-thioxanthene (VIa)

22.6 g (0.1 mol) of Compound Va was added to 250 ml of acetic anhydride, and the solution was cooled to 0 캜, and 43.6 g of bromine was dissolved in 25 ml of acetic acid. The reaction solution was further stirred at 0 ° C for 3 hours and then stirred at room temperature overnight. The resulting solid was filtered, washed with water, and then washed with cold methanol and dried to obtain 13 g of Compound VIa (yield: 34%).

¹ H NMR (CDCl ₃ , 500 Hz):? 7.61 (s, 2H), 7.3-7.2 (d, 4H)

7) Synthesis of 2,7-dibromo-9,9-diphenyl-9H-thioxanthene (VIb)

21.75 g (43%) of compound VIb was obtained in the same manner as in 6) except that 35 g (0.1 mol) of compound Vb was used instead of compound Va.

Mass: M ^{+ 1} = 509

8) Synthesis of 2,7-dibromo-9,9-dimethyl-9H-thioxanthene-10,10-dioxide (VIIa)

6.16 g (16 mmol) of compound VIa was dissolved in 50 ml of dichloromethane, and 9.86 g of metachloroperbenzoic acid was added at 0 占 폚 and stirred overnight. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure to remove the solvent. 60 ml of methanol was added to the concentrated residue, and the mixture was refluxed for 1 hour. The mixture was cooled to 0 deg. C, stirred for 2 hours, filtered and dried to obtain 6.5 g of Compound VIIa (yield: 83.8%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.04 (d, 2H), 7.88 (s, 2H), 7.65 (d, 2H), 1.87 (s, 6H)

9) Synthesis of 2,7-dibromo-9,9-diphenyl-9H-thioxanthene-10,10-dioxide (VIIb)

6.82 g (Yield: 79%) of compound (VIIb) was obtained in the same manner as in 8), except that 8.13 g of compound VIb was used instead of compound VIa.

Mass: M ^{+ 1} = 542

Synthesis Example 1 Synthesis of 9,9-dimethyl-2,7-bis (5H-pyrido [3,2- b] indol-5-yl) -9H-thioxanthene-10,10-

(10 mmol) of compound VIIa, 5.2 g (25 mmol) of 隆 -carboline, 8 g (60 mmol) of potassium carbonate, 70 mg of 1,2-diaminocyclohexane and 50 mg of CuI were successively added to 100 ml of xylene and the mixture was refluxed with stirring for 6 hours. The reaction solution was cooled, filtered, concentrated under reduced pressure, and then purified by column chromatography to obtain 3.8 g of the desired compound (yield: 45.5%).

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.68 (d, 2H), 8.55 (d, 4H), 8.05 (s, 2H), 7.80 ~ 7.84 (t, 4H), 7.59 ~ 7.63 (t, 2H ), 7.53-7.57 (d, 2H), 7.43-7.48 (d, 4H), 2.05 (s, 6H)

Mass: M ^{+ 1} = 591

Synthesis Example 2 Synthesis of 2,7-bis (8- (9H-carbazol-9-yl) -5H-pyrido [3,2- b] indol-5-yl) -9,9- Xanthene-10,10-dioxide

1) Synthesis of 8-bromo-5H-pyrido [3,2-b] indole

16.8 g of 5H-pyrido [3,2-b] indole and 20.28 g of N-bromosuccinimide were added to 150 ml of dichloromethane, followed by stirring at room temperature for 12 hours. The resulting mixture was stirred at room temperature for 2 hours, filtered, washed and dried to obtain 8-bromo-5H-pyrido [3,2-b] indole 21.1 g (yield: 85.7%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 9.92 (s, 1H), 8.53 (d, 1H), 8.25 (s, 1H), 7.97 (d, 1H), 7.52 (d, 1H), 7.42 (d, 1H), 7.25 (t, 1 H)

2) Synthesis of tert-butyl 8-bromo-5H-pyrido [3,2-b] indole-5-carboxylate

5.3 g of 8-bromo-5H-pyrido [3,2-b] indole, 3.15 g of 4-dimethylaminopyridine and 5.61 g of di-t-butyl dicarbonate were added to 150 ml of tetrahydrofuran and stirred overnight at room temperature. The reaction solution was filtered, washed and dried to obtain 5.6 g of tert-butyl 8-bromo-5H-pyrido [3,2-b] indole-5-carboxylate (yield: 75.5%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.63 (d, 1H), 8.35 (s, 1H), 8.07 (d, 1H), 7.62 (d, 1H), 7.63 (d, 1H), 7.35 (t, 1H), 1.25 (s, 9H)

3) Synthesis of 8- (9H-carbazol-9-yl) -5H-pyrido [3,2-b]

To 100 ml of xylene were added 3.5 g of tert-butyl 8-bromo-5H-pyrido [3,2-b] indole-5-carboxylate, 3.3 g of carbazole, 2.8 g of potassium carbonate, And 0.34 g of CuI were added in this order, and the mixture was refluxed and stirred for 6 hours. The reaction solution was filtered and concentrated under reduced pressure. Then, 100 ml of tetrahydrofuran and 20 ml of trifluoroacetic acid were added to the concentrated residue, stirred overnight at room temperature, and then filtered. The cake was added to 200 ml of distilled water and the pH was adjusted to 7.5, followed by filtration and drying to obtain 1.2 g of 8- (9H-carbazol-9-yl) -5H-pyrido [3,2- %).

¹ H NMR (DMSO-d ⁶ , 500 Hz):? 9.81 (s, IH), 8.55 (d, IH), 8.45 (d, 2H), 7.91 (d, 2H), 7.61-7.65 (d,

4) Synthesis of 2,7-bis (8- (9H-carbazol-9-yl) -5H-pyrido [3,2- b] indol-5-yl) -9,9- , 10-dioxide

except that 8.32 g (25 mmol) of 8- (9H-carbazol-9-yl) -5H-pyrido [3,2- b] indole was used in place of 8- 4.5 g (yield: 48.9%) of the compound was obtained.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.61 (d, 2H), 8.54 (d, 4H), 8.20 (d, 4H), 8.10 (d, 2H), 7.80 ~ 7.84 (t, 4H), 2H), 7.50 (d, 2H), 7.50 (d, 2H), 7.63 (d, 2H)

Mass: M ^{+ 1} = 921

Synthesis Example 3: Synthesis of 2,7-bis (8- (diphenylamino) -5H-pyrido [3,2- b] indol-5-yl) -9,9-dimethyl-9H-thioxanthene- - < / RTI >

1) Synthesis of N, N-diphenyl-5H-pyrido [3,2-b] indol-

5-pyrido [3,2-b] indol-8-amine was obtained in the same manner as in Synthesis Example 3, except that 3.1 g of diphenylamine was used in place of carbazole. (Yield: 44.7%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 9.95 (s, 1H), 8.51 (d, 1H), 7.48 (d, 1H), 7.21 ~ 7.32 (d, 5H), 6.91 ~ 6.89 (t, 2H), 6.75 ~ 6.82 (d, 3H), 6.65 ~ 6.63 (t, 4H)

2) Synthesis of 2,7-bis (8- (diphenylamino) -5H-pyrido [3,2- b] indol-5-yl) -9,9-dimethyl-9H-thioxanthene- Synthesis of seed

(25 mmol) of N, N-diphenyll-5H-pyrido [3,2-b] indol-8-amine instead of 8-carboline (Yield: 59.8%).

^{1 H NMR (DMSO-d 6} , 500Hz): 1 H NMR (CDCl 3, 500Hz): δ 8.65 (d, 2H), 8.60 (d, 4H), 8.30 (d, 4H), 8.20 (d, 2H) 2H), 7.30 (d, 4H), 7.91 (d, 2H), 7.91 (d, 2.08 (s, 6 H)

Mass: M ^{+ 1} = 925

Synthesis Example 4: Synthesis of 9,9-dimethyl-2,7-bis (8-phenyl-5H-pyrido [3,2- b] indol-5-yl) -9H-thioxanthene-10,10- synthesis

1) Synthesis of 8-phenyl-5H-pyrido [3,2-b] indole

3.5 g of tert-butyl 8-bromo-5H-pyrido [3,2-b] indole-5-carboxylate, 1.32 g of phenylboronic acid, 3.4 g of potassium carbonate, ) Palladium (0.23 g) and distilled water (8 ml) were added, and the mixture was refluxed and stirred for 6 hours.

After the reaction solution was cooled, dichloromethane (200 ml) and water (100 ml) were added to separate layers, and the organic layer was concentrated under reduced pressure. To the concentrated residue, 100 ml of tetrahydrofuran and 10 ml of trifluoroacetic acid were added, and the mixture was stirred at room temperature for 6 hours and filtered. The cake was added to 200 ml of distilled water and the pH was adjusted to 7.5, followed by filtration and drying to obtain 1.3 g of 8-phenyl-5H-pyrido [3,2-b] indole (yield: 53.27%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 9.95 (s, 1H), 8.63 (d, 1H), 8.35 (d, 1H), 8.07 (d, 1H), 7.68 (s, 1H), 7.63 (d, 4H), 7.35 (t, 3H)

Synthesis of 9,9-dimethyl-2,7-bis (8-phenyl-5H-pyrido [3,2- b] indol-5-yl) -9H-thioxanthene 10,10-

5.23 g of the title compound (yield: 70.4%) was obtained in the same manner as in Synthesis Example 1, except that 25 mmol of 8-phenyl-5H-pyrido [3,2-b] indole was used in place of 8-carboline.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.71 (d, 2H), 8.53 (d, 4H), 8.02 (s, 2H), 7.70 ~ 7.82 (t, 4H), 7.54 ~ 7.59 (t, 4H), (S, 2H), 7.41-7.38 (d, 6H), 2.08 (s, 6H)

Mass: M ^{+ 1} = 743

Synthesis Example 5: Synthesis of 2,7-bis (4- (5H-pyrido [3,2- b] indol-5-yl) phenyl) -9,9-dimethyl-9H-thioxanthene-10,10- Synthesis of

1) Synthesis of 5- (4-bromo) -5H-pyrido [3,2-b] indole

15 g of 5H-pyrido [3,2-b] indole, 38 g of 1-bromo-4-iodobenzene, 50 g of potassium carbonate and 11.5 g of copper were added to 190 ml of N, N-dimethylformamide and stirred at 120 ° C for 10 hours Respectively.

The reaction solution was cooled, filtered, and 6 L of purified water was slowly added to the filtrate, followed by stirring at room temperature for 2 hours and filtering. The cake was placed in 200 ml of methanol, refluxed and stirred for 2 hours, and then filtered to obtain 27.9 g (yield: 97%) of 5- (4-bromo) -5H-pyrido [3,2- b] indole.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.74 (d, 1H), 8.63 (d, 1H), 7.97 ~ 7.94 (d, 2H), 7.63 (d, 4H), 7.35 (t, 3H)

2) Synthesis of (4- (5H-pyrido [3,2-b] indol-5-yl) phenyl)

To a solution of 9.66 g of 5- (4-bromophenyl) -5H-pyrido [3,2-b] indole in 150 ml of tetrahydrofuran, the mixture was cooled to -78 ° C and 18.37 ml of n-butyllithium was slowly added thereto. After stirring at the same temperature for 1 hour, 4 g of 30% trimethylborate was slowly added, and the mixture was reacted at the same temperature for 2 hours and at room temperature for 1 hour.

The pH of the reaction solution was adjusted to 7 with a saturated aqueous ammonium chloride solution, followed by filtration and drying to obtain 6.4 g (yield: 83.7%) of the desired compound.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.74 (d, 1H), 8.63 (d, 1H), 8.10 ~ 8.17 (d, 2H), 8.10 ~ 8.17 (d, 4H), 7.35 (t, 3H )

3) Synthesis of 2,7-bis (4- (5H-pyrido [3,2-b] indol-5-yl) phenyl) -9,9-dimethyl-9H-thioxanthene-10,10-

4.13 g of Compound VII, 7.2 g of Compound c, 3.4 g of potassium carbonate, 0.23 g of tetrakis (triphenylphosphine) palladium and 8 ml of distilled water were added to 42 ml of toluene, and the mixture was stirred under reflux for 6 hours. After the reaction solution was cooled, dichloromethane (200 ml) and water (100 ml) were added to separate layers. The organic layer was concentrated under reduced pressure and then purified by column chromatography to obtain 2.67 g (yield: 36%) of the target compound.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.35 (d, 2H), 8.28 (d, 2H), 8.02 (s, 2H), 7.70 ~ 7.82 (t, 4H), 7.58 ~ 7.68 (t, 4H ), 7.54-7.59 (d, 4H), 7.49-7.50 (d, 4H), 7.45-7.43 (d,

Mass: M ^{+ 1} = 743

Synthesis Example 6 Synthesis of 9,9-dimethyl-2,7-bis (5H-pyrido [2,3-b] indol-5-yl) -9H-thioxanthene-10,10-

(yield: 56.7%) was obtained in the same manner as in Synthesis Example 1, except that 5.2 g (25 mmol) of? -carboline (Aldrich) was used instead of? -carboline.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.66 (d, 2H), 8.53 (d, 2H), 8.43 (d, 2H), 8.05 (s, 2H), 7.79 ~ 7.85 (t, 4H), 7.54 ~ 2H), 7.51-7.58 (d, 2H), 7.41-7.45 (d, 4H), 2.05 (s, 6H)

Mass: M ^{+ 1} = 591

Synthesis Example 7 Synthesis of 9,9-dimethyl-2,7-bis (5H-pyrido [3,4-b] indol-5-yl) -9H-thioxanthene-10,10-

6.04 g of the objective compound (yield: 65.4%) was obtained in the same manner as in Synthesis Example 1, except that 5.2 g (25 mmol) of β-carboline (Aldrich) was used instead of δ-carbolyne.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.68 (d, 2H), 8.55 (d, 2H), 8.45 (d, 2H), 8.05 (s, 2H), 7.80 ~ 7.84 (t, 4H), 7.54 ~ 2H), 7.55-7.54 (s, 2H), 7.45-7.48 (d, 4H), 2.05 (s, 6H)

Mass: M ^{+ 1} = 591

Synthesis Example 8 Synthesis of 9,9-dimethyl-2,7-bis (5H-pyrido [4,3-b] indol-5-yl) -9H-thioxanthene-10,10-

(yield: 48.2%) was obtained in the same manner as in Synthesis Example 1, except that 5.2 g (25 mmol) of? -carboline (Aldrich) was used instead of? -carboline.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.66 (d, 2H), 8.58 (s, 2H), 8.53 (d, 2H), 8.03 (s, 2H), 7.83 ~ 7.89 (t, 4H), 7.52 ~ 2H), 7.54-7.58 (d, 2H), 7.47-7.49 (d, 4H), 2.05 (s, 6H)

Mass: M ^{+ 1} = 591

Synthesis Example 9: Synthesis of 2- (9,9-dimethylacridine-10 (9H) -yl) -9,9-dimethyl- 7- (5H- pyrido [3,2- b] indol- -9H-thioxanthene-10,10-dioxide < / RTI >

1) Synthesis of 2-bromo-7- (9,9-dimethylacridine-10 (9H) -yl) -9,9-dimethyl-9H-thioxanthene-10,10-dioxide

To 90 ml of toluene were added 3.65 g of Compound VII, 2 g of 9,9-dimethyl-9,10-dihydroquercidine, 2.60 g of sodium t-butoxide, 8 mg of palladium acetate and 0.1 mg of t- Lt; / RTI > The reaction solution was cooled and filtered, and the filtrate was concentrated under reduced pressure and then purified by column chromatography to obtain 3.59 g (yield: 75%) of the target compound.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.35 (d, 2H), 7.95 (s, 1H), 7.86 (s, 1H), 7.56 (d, 2H), 7.44 (d, 4H), 7.12 (t, 4H), 1.86 (s, 6H), 1.62 (s, 6H)

2) Synthesis of 2- (9,9-dimethylacridine-10 (9H) -yl) -9,9-dimethyl- 7- (5H- pyrido [3,2- b] indol- Synthesis of thioxanthene-10,10-dioxide

5.9 g of 2-bromo-7- (9,9-dimethylacridine-10 (9H) -yl) -9,9-dimethyl-9H- thioxanthene 10,10- (Yield: 43%) of the objective compound was obtained by the same method as in Synthesis Example 1, except that 2.1 g of carboline was used.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.65 (d, 2H), 8.05 (s, 2H), 7.66 (d, 2H), 7.54 (d, 4H), 7.03 (t, 4H), 6.92 ( t, 3H), 6.22 (d, 4H), 1.86 (s, 6H), 1.62

Mass: M ^{+ 1} = 632

Synthesis Example 10: Synthesis of 2- (9H-carbazol-9-yl) -7- (9,9-dimethylacridine-10 (9H) -yl) -9,9- Synthesis of 10-dioxide

(yield: 55%) was obtained in the same manner as in Synthesis Example 9, except that 2.5 g of carbazole was used instead of 隆 -carboline.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.43 (d, 2H), 8.15 (s, 2H), 7.56 (d, 2H), 7.44 (d, 4H), 7.01 (t, 4H), 6.83 ( t, 4H), 6.12 (d, 4H), 1.84 (s, 6H), 1.65

Mass: M ^{+ 1} = 631

Synthesis Example 11 Synthesis of 2,7-di (9H-carbazol-9-yl) -9,9-dimethyl-9H-thioxanthene-10,10-

(yield: 60.9%) was obtained in the same manner as in Synthesis Example 1, except that 4.17 g (25 mmol) of carbazole was used instead of 隆 -carboline.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.52 (d, 2H), 8.18 (d, 4H), 8.09 (s, 2H), 7.83 (d, 2H), 7.535 (t, 8H), 7.45 ~ 7.41 ( d, 4H), 2.07 (s, 6H)

Mass: M ^{+ 1} = 589

Synthesis Example 12 Synthesis of 2,7-bis (3,6-di-tert-butyl-9H-carbazol-9-yl) -9,9-dimethyl-9H-thioxanthene-10,10-

The procedure of Synthesis Example 1 was repeated except for using 15.5 g (25 mmol) of 3,6-di-t-butyl-9H-carbazole instead of 8-carboline (yield: 41.1%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.68 (d, 2H), 8.55 (d, 4H), 8.05 (s, 2H), 7.80 ~ 7.84 (t, 4H), 7.59 ~ 7.63 (d, 2H), 7.43-7.48 (d, 4H), 2.05 (s, 6H), 1.45 (s, 36H)

Mass: M ^{+ 1} = 813

Synthesis Example 13 Synthesis of 2,7-bis (4- (9H-carbazol-9-yl) phenyl) -9,9-dimethyl-9H-thioxanthene-10,10-

1.85 g of the title compound (yield: 25%) was obtained in the same manner as in Synthesis Example 5, except that 7.2 g of Compound d was used instead of Compound c.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.30 (d, 2H), 8.18 (d, 2H), 8.12 (d, 2H), 8.02 (s, 2H), 7.70 ~ 7.82 (d, 4H), (D, 4H), 7.54-7.58 (t, 4H), 7.54-7.68 (t, 4H)

Mass: M ^{+ 1} = 741

Synthesis Example 14: Synthesis of 2,7-di (9H- [3,9'-bicarbazol] -9-yl) -9,9-dimethyl-9H-thioxanthene-10,10-

(yield: 37.5%) was obtained in the same manner as in Synthesis Example 1, except that 8.3 g (25 mmol) of 9H-3,9'-bicarbazole was used instead of 8-carboline.

^{1 H NMR (DMSO-d 6} , 500Hz)): δ 8.61 (d, 4H), 8.44 (d, 4H), 8.15 (d, 4H), 8.08 (s, 2H), 7.70 (t, 4H), 7.62 2H), 7.52 (d, 2H), 7.50 (t, 4H), 7.43 (d, 4H), 7.25

Mass: M ^{+ 1} = 919

Synthesis Example 15 Synthesis of 2,7-bis (9,9-dimethylacridine-10 (9H) -yl) -9,9-dimethyl-9H-thioxanthene-10,10-

To 90 ml of toluene was added 3.65 g of compound VII, 4 g of 9,9-dimethyl-9,10-dihydrolaccridine, 5.22 g of sodium t-butoxide, 17 mg of palladium acetate and 0.2 mg of t- Lt; / RTI > The reaction solution was cooled and filtered, and the filtrate was concentrated under reduced pressure and then purified by column chromatography to obtain 4.2 g (yield: 71%) of the target compound.

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.5 (d, 2H), 8.00 (s, 2H), 7.66 (d, 2H), 7.54 (d, 4H), 7.02 (t, 4H), 6.96 (t, 4H), 6.24 (d, 4H), 1.88 (s, 6H), 1.65 (s, 12H)

Mass: M ^{+ 1} = 673

Synthesis Example 16 Synthesis of 9,9-dimethyl-2,7-di (10H-phenothiazin-10-yl) -9H-thioxanthene-10,10-

(Yield: 53.9%) was obtained in the same manner as in Synthesis Example 15, except that 3.65 g (8.8 mmol) of Compound VII and 3.8 g (19.13 mmol) of 10H-phenothiazine were used in 90 ml of toluene.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.41 (d, 2H), 7.96 (s, 2H), 7.62 (d, 2H), 7.50 (d, 4H), 6.95 (t, 4H), 6.92 ( t, 4H), 6.20 (d, 4H), 1.81 (s, 6H)

Mass: M ^{+ 1} = 653

Synthesis Example 17: Synthesis of 9,9-dimethyl-2,7-di (10H-phenoxazin-10-yl) -9H-thioxanthene-10,10-

(Yield: 53%) was obtained in the same manner as in Synthesis Example 15, except for using 3.65 g (8.8 mmol) of Compound VII and 3.25 g (19.13 mmol) of 10H-phenoxane in 90 ml of toluene.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.43 (d, 2H), 7.98 (s, 2H), 7.64 (d, 2H), 7.53 (d, 4H), 6.98 (t, 4H), 6.95 ( t, 4H), 6.25 (d, 4H), 1.87 (s, 6H)

Mass: M ^{+ 1} = 621

Synthesis Example 18: Synthesis of 2- (9,9-dimethylacridine-10 (9H) -yl) -9,9-dimethyl- 7- (10H-phenothiazin-10-yl) -9H-thioxanthene-10 , 10-dioxide

2.38 g of the objective compound (yield: 35.9%) was obtained in the same manner as in Synthesis Example 9, except that 2.6 g of 10H-phenothiazine was used in place of 8-carboline.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.47 (d, 2H), 8.02 (s, 2H), 7.68 (d, 2H), 7.56 (d, 4H), 7.05 (t, 4H), 6.98 ( t, 4H), 6.24 (d, 4H), 1.88 (s, 6H), 1.62

Mass: M ^{+ 1} = 663

Synthesis Example 19 Synthesis of 2,7-bis (9,9-diphenylacridine-10 (9H) -yl) -9,9-dimethyl-9H-thioxanthene-10,10-

Synthesis Example 15 was repeated except that 6.9 g (Almadis chemical, 19.13 mmol) of 9,9-diphenyl-9,10-dihydroacridine was used instead of 9,9-dimethyl-9,10- 3.6 g of the aimed compound was obtained by the same method (yield: 45%).

_{^{1 H NMR (CDCl 3, 500Hz}} ): δ 8.29 (d, 2H), 7.44 (s, 2H), 7.37 ~ 7.26 (m, 14H), 7.19 ~ 7.03 (t, 4H), 6.98 ~ 6.94 (t, 8H ), 6.83 (d, 8H), 6.4 (d, 4H), 1.67 (s, 6H)

Mass: M ^{+ 1} = 921

Synthesis Example 20 Synthesis of 2,7-bis (9,9-diphenylacridine-10 (9H) -yl) -9,9-diphenyl-9H-thioxanthene-10,10-

(Yield: 65%) was obtained in the same manner as in Synthesis Example 19, except that 4.75 g (8.8 mmol) of Compound VIIb was used in place of Compound VIIa.

^{1 H NMR (DMSO-d 6} , 500Hz): δ 8.34 (d, 2H), 7.41 (s, 2H), 7.33 ~ 7.27 (m, 18H), 7.25 ~ 7.07 (t, 8H), 6.85 ~ 6.79 (t , 10 H), 6.67 (d, 8 H), 6.52 (d, 4 H)

Mass: M ^{+ 1} = 1045

Example 2: Evaluation of characteristics of organic light emitting device

The glass substrate on which the ITO thin film was formed to a thickness of 50 nm was washed, dried and mounted on the substrate holder of the vacuum deposition equipment. (HIL) / hole transport layer (HTL) / exciton blocking layer (EBL) / organic light emitting layer (EML) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) on the ITO thin film EIL) / Cathode were sequentially deposited by thermal evaporation. In the organic luminescent layer, the compound of the present invention is contained in an amount of 40% Lt; / RTI &gt; The thickness of each layer and the material constituting each layer are shown in Table 1 below. The structure of the constituent material constituting each layer is shown in Fig. Once the deposition of all layers was completed, encapsulation was carried out with a glass lid sealed with epoxy resin in a nitrogen glove box (<1 ppm H ₂ O and O ₂ ), and the moisture getter was introduced into the package to complete the device.

The characteristics of the organic light emitting device fabricated by the above method according to the dopant were evaluated, and the results are shown in Table 2.

FIGS. 2 to 4 show graphs showing driving voltage, external quantum efficiency, and maximum emission wavelength, respectively, for a device doped with the compound of Synthesis Example 19, which has excellent luminous efficiency. For comparison, the same device was fabricated by DMAC-DPS, which is a non-cyclic sulfone compound, and the driving voltage, luminous efficiency and maximum emission wavelength were measured and the results are also shown. The structure of DMAC-DPS is described in the graph of FIG. Table 3 also shows the characteristics of the device doped with the compound of Synthesis Example 19. The figures show that the compounds of the present invention are similar to the non-cyclized sulfonic compounds in the driving voltage, but show a significant increase in the external luminous efficiency. It can also be seen that the maximum emission wavelength emits light of a shorter wavelength due to the blue transition.

Claims (7)

Lt; RTI ID = 0.0 &gt; (1) &lt; / RTI &gt;

[Chemical Formula 1]
Here, R ₁ and R ₂ may be the same or different from each other, and may be a pyridone ring, a phenyl group, a carbazole group, a 9,9-dimethyl-9,10-dihydraacridine group, a 10H- And R ₃ is a methyl group or a phenyl group.
The method according to claim 1,
Wherein the pyridoyl group, the phenyl group or the carbazole group has a substituent of an alkyl group, a carbazole group, a phenyl group or a diphenylamino group.
3. The method according to claim 1 or 2,
The compound is preferably selected from the group consisting of 9,9-dimethyl-2,7-bis (5H-pyrido [3,2- b] indol-5-yl) -9H-thioxanthene-10,10- (9- (9H-carbazol-9-yl) -5H-pyrido [3,2- b] indol-5-yl) -9,9-dimethyl- 9H-thioxanthene-10,10- Pyridyl [3,2-b] indol-5-yl) -9,9-dimethyl-9H-thioxanthene-10,10-dioxide, (8-phenyl-5H-pyrido [3,2-b] indol-5-yl) -9H-thioxanthene-10,10-dioxide, 2,7- Yl) phenyl) -9,9-dimethyl-9H-thioxanthene-10,10-dioxide, 9,9-dimethyl-2 , 7-bis (5H-pyrido [2,3-b] indol-5-yl) -9H-thioxanthene-10,10-dioxide, 9,9- Pyrido [4,3-b] indol-5-yl) -9H-thioxanthene-10,10-dioxide, 9,9- (9H-indol-5-yl) -9H-thioxanthene-10,10-dioxide and 2- (9,9-dimethylacridine- -9H-thioxanthene-10,10-dioxide, 2- (9H-carbazol-9-yl) -7- (9,9- (9H-carbazol-9-yl) -9,9-dimethyl-9H-thioxanthene-10,10- -Dimethyl-9H-thioxanthene-10,10-dioxide, 2,7-bis (3,6-di-tert- butyl-9H-carbazol- (9H-carbazol-9-yl) phenyl) -9,9-dimethyl-9H-thioxanthene-10,10-dioxide, 2, (9H- [3,9'-bicarbazol] -9-yl) -9,9-dimethyl-9H-thioxanthene-10,10-dioxide, 2,7- Dimethylacridine-10 (9H) -yl) -9,9-dimethyl-9H-thioxanthene-10,10-dioxide, 9,9- -yl) -9H-thioxanthene-10,10-dioxide, 9,9-dimethyl-2,7-di (10H- - (9,9-dimethylacridine-10 (9H) -yl) -9,9-dimethyl- 7- (10H-phenothiazin-10-yl) -9H- thioxanthene 10,10- (9,9-diphenylacridine-10 (9H)) - 9,9-dimethyl-9H-thioxanthene-10,10-dioxide, 2,7- 10 (9H) -yl) -9,9-diep &lt; / RTI &gt; -9H-thioxanthene-10,10-dioxide. &Lt; / RTI &gt;
3. The method according to claim 1 or 2,
Wherein said compound exhibits thermal activation delayed fluorescence by inverse intercalation.
An organic light emitting device comprising an anode, a cathode, and an organic light emitting layer interposed between the anode and the cathode,
The organic light emitting device according to claim 1 or 2, wherein the compound is included in the organic light emitting layer.
6. The method of claim 5,
A compound of claim 1 or 2 is included as a dopant,
Wherein the organic light emitting device further comprises a phosphorescent material as a host.
The method according to claim 6,
Wherein at least one of the excited triplet energies and excited triplet energies of the phosphorescent material has a higher value than the excited triplet energy of the dopant.

Images