KR101800666B1 - Metanodiazocine derivatives having carbazole group and organic electroluminescent devices including the same - Google Patents

Abstract

The present invention relates to a methanodiazocine derivative and an organic electroluminescent device including the same, and more specifically, the present invention provides a methanodiazocine derivative having a carbazole functional group, which is a novel blue light emitting compound and can be usefully used in a light emitting layer of an organic electroluminescent device, on both sides; and an organic electroluminescent device comprising the same.

Description

TECHNICAL FIELD The present invention relates to a methanodiazocine derivative having a carbazole group and an organic electroluminescent device including the same,

The present invention relates to a methanodiacosin derivative and an organic electroluminescent device comprising the same. More particularly, the present invention relates to a 5'-methanodialyl [b , f] [1,5] diazocine derivatives and organic electroluminescent devices comprising the same.

An organic electroluminescent device (organic EL device) capable of being driven by a self-luminous type and capable of driving at a low voltage has a better viewing angle and contrast ratio than a liquid crystal display (LCD), which is a mainstream of a flat panel display device. It can be thinned, and it is advantageous in terms of power consumption. In addition, the response speed is fast and the color reproduction range is wide, and it is attracting attention as a next generation display device and is used as a display for a smart phone and a TV.

In general, an organic EL element is formed on a glass substrate in the order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode in this order. The organic thin film may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (ETL) in addition to an emission layer (EIL), and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) in light emission characteristics of the light emitting layer.

When an electric field is applied to the organic EL device having such a structure, holes are injected from the anode and electrons are injected from the cathode. The injected holes and electrons are recombined in the light emitting layer through the hole transporting layer and the electron transporting layer, . The luminescent excitons thus formed emit light while transitioning to ground states. At this time, luminescent dyes (guest dopants) are doped in the light emitting layer (host) to increase the efficiency and stability of the luminescent state.

In recent years, it has been known that not only a fluorescent light emitting material but also a phosphorescent emitting material can be used as a light emitting material of an organic EL device. Such phosphorescent emitting is a phenomenon in which electrons are transferred from a ground state to an excited state, A singlet exciton is a non-luminescent transition to a triplet exciton, and then a triplet exciton is a mechanism for emitting light while transitioning to a bottom state. In this case, the triplet exciton can not transition directly to the ground state at the time of transition (spin forbidden), and after the electron spin flipping proceeds, it undergoes a transition to the ground state, so that the lifetime (lifetime) . That is, the emission duration of fluorescence emission is only several nanoseconds, but in the case of phosphorescence, it corresponds to a relatively long time of several microseconds.

Further, researches for improving the luminous efficiency using a thermally activated delayed fluorescence have been developed.

Korean Patent Publication No. 2011-0092262

The present invention provides a methanedioxosin derivative having a carbazole group having excellent luminous efficiency, long life and high color purity, which is employed in a light emitting layer of an organic electroluminescent device, and an organic electroluminescent device comprising the same.

The present invention provides a methanodiacosin derivative having a carbazol group as a substituent, which can be used as a host and a dopant for blue luminescence having excellent properties, and the novel metanodiacosin derivative of the present invention is represented by the following general formula 2.

[Chemical Formula 1]

(2)

(In the formulas (1) and (2)

,

또는

이며;T is

,

or

;

L ₁ to L ₆ are independently of each other a single bond or (C 6 -C 30) arylene;

Y ₁ to Y ₄ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl,

R ₁ and R ₂ are, independently of each other, (C 6 -C 30) aryl;

The aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, nitro, (C 1 -C 30) alkyl, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl. )

The present invention also provides an organic electroluminescent device comprising the methanodiacosine derivative of the present invention.

The methanodiacosin derivative of the present invention has metanodiacosine skeleton as a core, and an organic electroluminescent device including a carbazole functional group as a substituent, improves electrical stability and lifetime characteristics, and can emit light at a high luminance And exhibits excellent luminous efficiency and color purity.

1 is a diagram showing the UV absorbance and the PL intensity spectrum of the compounds KKY23, KKY24, KKY26, KKY27 and KKY30 of the present invention.
Figure 2 is a graph showing the UV absorbance and the PL intensity spectrum of the compounds KKY26 and KKY27 of the present invention.
3 is a graph showing the IVL characteristics of the compounds KKY26 and KKY27 of the present invention.
4 is a graph showing the luminance efficiency-current density characteristics of the compounds KKY26 and KKY27 of the present invention.
5 is a graph showing the quantum efficiency-current density characteristics of the compounds KKY26 and KKY27 of the present invention.
6 is a diagram showing EL and Film PL spectra of a device of compound KKY24 of the present invention.
Figure 7 is a diagram showing the EL and Film PL spectra of a device of compound KKY26 of the present invention.
Figure 8 shows the EL and Film PL spectra of a device of compound KKY27 of the present invention.

The present invention provides a methanodiacosine derivative having a carbazole group as a substituent, which can be used as a host for blue luminescence having excellent properties and a dopant, wherein the methanedioxosin derivative having a novel carbazole group of the present invention is represented by the following general formula Or represented by the following formula (2).

[Chemical Formula 1]

(2)

(In the formulas (1) and (2)

,

또는

이며;T is

,

or

;

L ₁ to L ₆ are independently of each other a single bond or (C 6 -C 30) arylene;

Y ₁ to Y ₄ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl,

R ₁ and R ₂ are, independently of each other, (C 6 -C 30) aryl;

The aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, nitro, (C 1 -C 30) alkyl, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl. )

The methanodiacosin derivative having a carbazole group of the present invention as a substituent, specifically 5,11-methanodialo [b, f] [1,5] diazocine derivative, has a central skeleton of 5,11-methanodialyl [b, f] [1,5] diazocine, and the carbazole group on both sides of the central skeleton, 5,11-methanodialyl [b, f] [1,5] diazocine, An organic electroluminescent device having improved luminous efficiency and excellent lifespan characteristics and excellent driving life of the device, leading to an increase in power efficiency and improved power consumption.

In addition, the Y ₁ to Y ₄ in formula (I) and formula (2) is of the present invention meth furnace dia terazosin derivatives are independently hydrogen, (C6-C30) aryl or (C3-C30), and heteroaryl each other, Y ₁ to Y ₄ Aryl and heteroaryl may be further substituted with any one or more selected from cyano, (C6-C30) aryl and (C3-C30) heteroaryl.

The organic electroluminescent device employing the carbazole group substituted for both of the 5,11-methanodialyl [b, f] [1,5] diazocine, which is the central skeleton of the present invention, It has improved characteristics.

In the present invention, Y ₁ and Y ₄ and Y ₂ and Y ₃ are each independently hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) alkyl, ) Heteroaryl, and the aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl; Formula in 2 Y ₁ and Y ₂ are the same as each other are hydrogen, (C6-C30) aryl or (C3-C30), and heteroaryl, Y ₁ aryl and heteroaryl of 1 to Y ₂ is cyano, (C6-C30) aryl And (C3-C30) heteroaryl; R ₁ and R ₂ may be the same (C6-C30) aryl.

In view of luminous efficiency, R ₁ and R ₂ in Formula 2 of the present invention may be independently phenyl, diphenyl or naphthalenyl.

 Preferably, Formula 1 is represented by Formula 3 or Formula 3-1, and Formula 2 may be represented by Formula 4 or Formula 4-1.

(3)

[Formula 3-1]

[Chemical Formula 4]

[Formula 4-1]

(In the above formulas 3, 3-1, 4 and 4-1,

,

또는

이며;T is

,

or

;

L ₁ to L ₆ are independently of each other a single bond or (C 6 -C 30) arylene;

Y ₁ to Y ₄ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl,

R ₁ and R ₂ are, independently of each other, (C 6 -C 30) aryl;

The aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl.

From the viewpoint of excellent light-emitting efficiency and color purity, it is preferable to use the above-mentioned chemical formula 3 and chemical formula 4.

In the above formulas (3), (3-1), (4) and (4-1), L ₁ to L ₆ may independently be a single bond or may be selected from the following formulas.

(Wherein R ₁₁ and R ₁₂ are hydrogen or (C 6 -C 30) aryl, o is an integer of 1 to 4, and when o is an integer of 2 or more, R ₁₁ and R ₁₂ may be the same or different from each other.

More preferably, R ₁₁ and R ₁₂ in the general formulas (3), (3-1), (4) and (4-1) may be hydrogen, phenylene, naphthalenylene or anthracenylene.

Preferably, L ₁ to L ₂ in the general formulas (3) and (3-1) according to an embodiment of the present invention are single bonds or (C 6 -C 30) arylene. L ₃ and L ₅ or L ₄ and L ₆ are each independently a single bond or (C 6 -C 30) arylene; Y ₁ to Y ₄ are independently hydrogen, (C6-C30) aryl or (C3-C30), and heteroaryl each other, aryl and heteroaryl of Y ₁ to Y ₄ is cyano, (C6-C30) aryl and (C3 -C30) heteroaryl, more preferably L ₁ and L ₂ , L ₃ and L _5, or L ₄ and L ₆ are the same as each other, In addition,

(Wherein R ₁₁ and R ₁₂ are hydrogen or (C 6 -C 30) aryl, o is an integer of 1 to 4, and when o is an integer of 2 or more, R ₁₁ and R ₁₂ may be the same or different from each other.

Y ₁ and Y ₃ and Y ₂ and Y ₄ are each independently hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl, the aryl and heteroaryl of Y ₁ to Y ₄ are cyano, -C30) aryl and (C3-C30) heteroaryl group which has one or more may be further substituted with, as is more preferably Y ₁ and Y ₃ are the same as each other are hydrogen, (C6-C30) is selected from aryl or (C3- C30) a heteroaryl group, Y ₁ and Y ₃ of the aryl and heteroaryl is cyano, (C6-C30) aryl and (C3-C30) may be further substituted with at least one selected from heteroaryl, and Y ₂ and Y ₄ can be hydrogen.

Preferably, in the above formula (4) and 4-1, respectively in the above formula (IV) L ₁ and L ₂ or L ₃ and L ₄ is equal to a single bond or (C6-C30) arylene, and each other; Y ₁ and Y ₂ are each independently hydrogen or (C 6 -C 30) aryl, and R ₁ and R ₂ may be independently (C 6 -C 30) aryl.

L ₁ to L ₆ in the general formulas (1) and (2) are independently a single bond, phenylene, biphenylene, naphthalenylene, anthracenylene, phenylene atracenylene Y ₁ to Y ₄ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl, and aryl and heteroaryl of Y ₁ to Y ₄ are cyano, nitro , (C1-C30) alkyl, (C6-C30) aryl and (C3-C30) heteroaryl.

The methanodiacosin derivatives of the above formulas (1) and (2) of the present invention can be selected from the following compounds, but are not limited thereto.

&Quot; Alkyl " as used in the present invention means a linear or branched hydrocarbon radical having 1 to 30 carbon atoms.

도 아릴에 포함된다.&Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, . The naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl includes 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl,

Are also included in the aryl.

"Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.

The '(C 1 -C 30) alkyl' group described in the present invention is preferably (C 1 -C 20) alkyl, more preferably (C 1 -C 10) alkyl, and the ' (C6-C20) aryl, and the '(C3-C30) heteroaryl' group is preferably (C3-C20) heteroaryl.

The methanodiacosine derivative of the present invention can be synthesized as long as it can be recognized by a person skilled in the art and can be prepared, for example, as shown in the following Schemes 1 to 3.

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

(Wherein T, L ₁ to L ₄ , Y ₁ to Y ₂ and R ₁ are the same as defined in the above formula (1), and L is the same as defined in the above formulas (L ₁₎ to (L ₂ )).

The present invention also provides an organic electroluminescent device comprising the methanodiacosine derivative of the present invention.

The methanodiacosin derivative of the present invention can be used alone or in combination with other organic luminescent compounds for use in organic electroluminescent devices.

Preferably, the methanedioxane derivative of the present invention may be included in the light emitting layer of the organic electroluminescent device, and more preferably, it may be used as a host material of the light emitting layer.

The organic electroluminescent device of the present invention can be manufactured by a conventional method that can be recognized by a person skilled in the art and includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer comprises at least one methanedioxane derivative represented by the formula (1). The organic material layer may include a light emitting layer, and the methanodiacosin derivative represented by Formula 1 of the present invention may be used as a host material in the light emitting layer.

The organic electroluminescent device of the present invention includes a hole injecting layer (HIL), a hole transporting layer (HTL), a light emitting layer (EML), an electron transporting layer (ETL), an electron injecting layer (EIL), etc., between an anode and a cathode And an anode electrode material is deposited on the substrate to form an anode. At this time, the substrate to be used may be a substrate used in a conventional organic electroluminescent device. In particular, a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, good. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity can be used. The anode electrode material may be deposited by a conventional anode formation method, and a specific example thereof may be a deposition method or a sputtering method.

Then, a hole injecting layer material may be formed on the anode electrode by a method such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) method, etc., It is preferable to form it by the vacuum evaporation method from the viewpoint of difficulty. When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and thermal properties of the desired hole injection layer, and the like. In general, the deposition temperature is 50-500 [ 10 to a degree of vacuum of 10 ^-3 torr, vapor deposition rate of 0.01 to 100 Å / sec, can be selected in the layer thickness range from 10 Å to 5 ㎛.

The hole injection layer material is not particularly limited, but a phthalocyanine compound such as copper phthalocyanine or TCTA (4,4 ', 4 "-tri (N-carbazolyl) triphenylamine) as an amine derivative, m-MTDATA (4, M-MTDAPB (4,4 ', 4 "-tris (3-methylphenylamino) phenoxybenzene), HI-406 (N1, N1' - (biphenyl-4,4'-diyl) bis (N1- (naphthalen-1-yl) -N4, N4-diphenylbenzene-1,4-diamine).

Next, a hole transporting layer material may be formed on the hole injection layer by a method such as a vacuum deposition method, a spin coating method, a casting method, a LB method, or the like. In this case, since uniform film quality can be easily obtained, It may be preferable to be formed by a vapor deposition method. When the hole transport layer is formed by the vacuum deposition method, the deposition conditions are different depending on the compound used, but generally, the conditions can be selected within substantially the same range as the formation of the hole injection layer.

The hole transport layer material is not particularly limited and may be selected from among conventionally known materials used for the hole transport layer. Specific examples thereof include carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N , N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'- diamine (TPD) ) -N, N'-diphenylbenzidine (? -NPD), and the like can be used.

Next, a light emitting layer material may be formed on the hole transporting layer by a method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or the like, and a vacuum deposition method may be used to form a uniform film, . When the light emitting layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used, but it is generally preferable to select the deposition conditions within the substantially same range as the formation of the hole injection layer. In addition, the material used for the light emitting layer may be a metanodiaceosin derivative represented by Formula 1 or Formula 2 of the present invention as a blue host material.

When the metanodiaceosin derivative of the present invention is used as a blue luminescent host, a phosphorescent or fluorescent dopant may be used together to form a luminescent layer. In this case, any fluorescent dopant can be used as long as it is a commonly used material, and for example, N12-bis (3,4-dimethylphenyl) -N6, N12-dimethyisilclycine-6,12-diamine) , Phosphorescent dopants such as Ir (ppy) 3 (tris (2-phenylpyridine) iridium), a green phosphorescent dopant, and F2Irpic (iridium (III) bis [4,6-difluorophenyl) N, C2 '] picolinate) or the like can be vacuum-deposited (doped). The doping concentration of the dopant is not particularly limited, but is preferably doped with 0.01 to 15 parts by weight of the dopant relative to 100 parts by weight of the host.

When the phosphorescent dopant is used together with the phosphorescent dopant, it is preferable to further laminate the hole blocking material (HBL) by a vacuum evaporation method or a spin coating method in order to prevent the triplet exciton or hole from diffusing into the electron transporting layer. The hole blocking material which can be used at this time is not particularly limited, but a known material used as the hole blocking material can be arbitrarily selected and used. For example, oxadiazole derivatives or triazole derivatives, phenanthroline derivatives, Balq (bis (8-hydroxy-2-methylquinolinonato) -aluminum biphenoxide), or phenanthrolines Etc. may be used.

An electron transport layer is formed on the light emitting layer formed as described above. The electron transport layer is formed by a vacuum deposition method, a spin coating method, a casting method, or the like, and is preferably formed by a vacuum deposition method.

Examples of the electron transport layer material include quinoline derivatives, particularly tris (8-quinolinolato) aluminum (Alq3), and the like. The electron transport layer material serves to stably transport electrons injected from the electron injection electrode. ), Or ET4 (6,6 '- (3,4-dimemethyl-1,1-dimethyl-1H-silanol-2,5-diyl) di-2,2'-bipyridine). In addition, an electron injection layer (EIL), which is a material having a function of facilitating the injection of electrons from the cathode, may be laminated on the electron transport layer. Examples of the electron injection layer material include LiF, NaCl, CsF, Li ₂ O, BaO Can be used.

Then, an electron injection layer material may be formed on the electron transport layer by a vacuum deposition method, a spin coating method, a casting method, or the like. Finally, a metal for cathode formation may be formed on the electron injection layer by vacuum deposition, sputtering Method, and used as a cathode. At this time, as the metal for forming the cathode, a metal, an alloy, an electrically conductive compound having a low work function, and a mixture thereof can be used. Specific examples thereof include Li, Mg, Al, Al-Li, Ca, Mg-In, Mg-Ag, . Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

The organic light emitting device of the present invention can have an organic light emitting device having various structures as well as an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode structure, Layer or an intermediate layer of two layers may be further formed.

Hereinafter, for better understanding of the present invention, the methanodiacosin derivative of the present invention, the method for producing the same, and the luminescent characteristics of the device are described for the representative compounds of the present invention, The scope of the present invention is not limited thereto.

[Production Example 1]

( 5S, 11S ) - 2,8- Dibromo -6,12- dihydro -5,11-methanodibenzo [b, f] [1,5] diazocine (A)

 Paraformaldehyde (3.49 g, 116 mmol) was added to a mixture of trifluoroacetic acid (50 ml) and 4-bromoanilne (10 g, 58 mmol) at 0 ° C and refluxed for 48 hours. Ammonium hydroxide was added to adjust pH to 14. Water was added, and the mixture was stirred for 30 minutes and extracted with dichloromethane. After drying with sodium sulfate (anhydrous), the solvent was removed under reduced pressure, and recrystallized with ethanol to obtain Compound A (7.69 g, 70%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.42 (d, 2H), 7.20 (s, 2H), 6.82 (d, 2H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 ( d, 2H); Anal. Calcd. _{for C 15 H 12 Br 2 N} 2 (%): C, 47.40; H, 3.18; N, 7.37. Found: C, 47.12; H, 3.32; N, 7.19.

[Production Example 2]

Preparation of (5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (B)

4-iodoaniline (20 g, 91.3 mmol) was added to trifluoroacetic acid (100 ml), and the temperature was lowered to 0 ° C. Paraformaldehyde (5.4 g, 182.8 mmol) was added thereto and stirred for 48 hours. After removing half of the solvent under reduced pressure, ammonium hydroxide (200 ml) was added to adjust the pH to 14. Water (1000 ml) was added, stirred for 30 minutes, extracted with dichloromethane, and the organic layer was separated. The organic layer was dried with sodium sulfate (anhydrous), and the solvent was removed under reduced pressure. The residue was recrystallized from ethanol to obtain Compound B (15.32 g, 70.8%) as a yellow solid.

^{1 H NMR (400 MHz, CDCl} 3): δ 7.42 (d, 2H), 7.21 (s, 2H), 6.89 (d, 2H), 4.62 (d, 2H), 4.27 (s, 2H), 4.05 (s , 2H); Anal. Calcd. _{for C 15 H 12 N 2 I} 2 (%): C, 38.00; H, 2.55; N, 5.91. Found: C, 37.81; H, 2.69; N, 6.11.

[Production Example 3]

Preparation of (5S, 11S) -2,8-bis (10-bromoanthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

 (5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [l, , 5] diazocine (5.25 g, 11.07 mmol), (10-bromoanthracen-9-yl) boronic acid (7 g, 23.26 mmol), tetrakis (triphenylphosphine) palladium 6.2 g, 44.85 mmol), and the mixture was refluxed for 18 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous). The solvent was removed under reduced pressure and the residue was recrystallized from hexane / dichloromethane = 1: 1 to obtain Compound C (6.53 g, 80.6%) as a yellow solid.

¹ H NMR (400 MHz, CDCl ₃ ): 8.07 - 8.05 (d, 4H), 7.98-7.95 (m, 6H), 7.55-7.49 (m, 6H), 7.48-7.45 , 2H), 4.23 (s, 2H), 4.01 (s, 2H). Anal. Calcd. for C ₄₃ H ₂₈ Br ₂ N ₂ (%): C, 70.51; H, 3.85; N, 3.82. Found: C, 70.22; H, 3.98; N, 3.59.

[Production Example 4]

Preparation of (5S, 11S) -2,8-bis (2-bromophenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (D)

(5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] was dissolved in a mixed solution of toluene (160 ml), ethanol (60 ml) (8 g, 41.3 mmol), tetrakis (triphenylphosphine) palladium (0) (1 g, 0.86 mmol) and potassium carbonate (8 g, 18.9 mmol) , 58 mmol) and refluxed for 18 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extracting with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and the solvent was removed by decompression. Hexane / ethylacetate = 3: 1 solution to obtain a solid compound D (5.76 g, 57.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ 7.72 - 7.70 (m, 4H), 7.44 - 7.40 (m, 6H), 7.21 - 7.10 (m, 4H), 4.62 (d, 2H), 4.27 (s, 2H), 4.05 (s, 2H). Anal. Calcd. for C ₂₇ H ₂₀ N ₂ Br ₂ (%): C, 60.93; H, 3.79; N, 5.26. Found: C, 60.72; H, 4.03; N, 5.43

[Production Example 5]

Preparation of (5S, 11S) -2,8-bis (3-bromophenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (E)

(5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine was added to a mixed solution of dioxane (80 ml) (3 g, 6.33 mmol) and (3-bromophenyl) boronic acid (2.93 g, 14.56 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extracting with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and the solvent was removed by decompression. Ethanol, and recrystallized with Hexane: Ethyl Acetate = 1: 1 to obtain the title compound E (1.76 g, 52%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.78 - 7.42 (m, 8H), 7.39 - 7.10 (m, 6H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H ); Anal. Calcd. for C ₂₇ H ₂₀ Br ₂ N ₂ (%): C, 60.93; H, 3.79; N, 5.26. Found: C, 60.58; H, 4.08; N, 5.19.

[Production Example 6]

Preparation of (5S, 11S) -2,8-bis (4-bromophenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (F)

The Dioxane (80 ml) and water (10 ml) into the mixture solution (5S, 11S) - 2,8- diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (3 g, 6.33 mmol) and (4-bromophenyl) boronic acid (2.93 g, 14.56 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extracting with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and the solvent was removed by decompression. Ethanol, and recrystallized with Hexane: Ethyl Acetate = 1: 1 to obtain Compound F (1.89 g, 56%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.78 - 7.42 (m, 8H), 7.39 - 7.10 (m, 6H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H ); Anal. Calcd. for C ₂₇ H ₂₀ Br ₂ N ₂ (%): C, 60.93; H, 3.79; N, 5.26. Found: C, 60.72; H, 4.14; N, 5.09.

[Production Example 7]

Preparation of (5S, 11S) -2,8-bis (4-bromonaphthalen-1-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

The Dioxane (80 ml) and water (10 ml) into the mixture solution (5S, 11S) - 2,8- diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.37 g, 0.317 mmol), and potassium carbonate (3.5 g, 6.3 mmol), (4-bromonaphthalen-1-yl) boronic acid (3.97 g, 15.8 mmol), tetrakis (triphenylphosphine) palladium 25.32 mmol) was added thereto and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extracting with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and the solvent was removed by decompression. Ethanol, and recrystallized with Hexane: Ethyl Acetate = 3: 1 to obtain Compound G (2.53 g, 63%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.69 - 7.67 (d, 6H), 7.60 - 7.55 (m, 2H), 7.47 - 7.45 (m, 8H), 7.34 - 7.31 (m, 2H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H); Anal. Calcd. for C ₃₅ H ₂₄ Br ₂ N ₂ (%): C, 66.47; H, 3.83; N, 4.43. Found: C, 66.18; H, 4.08; N, 4.19

[Production Example 8]

Preparation of 2,8-bis (3-bromo-9H-carbazol-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (H)

To a solution of 2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (2.83 g, 5.97 mmol), 3-bromo-9H-carbazole (1.86 g, 5.34 mmol), copper (I) oxide (2.56 g, 17.89 mmol) and potassium carbonate (2.48 g, 17.94 mmol) were added and refluxed for 18 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. The solid product H (3.05 g, 72%) was obtained by recrystallization from hexane: dichloromethane = 1: 1 solution.

¹ H NMR (400 MHz, CDCl ₃ ):? 8.46 (s, 2H), 7.98-7.95 (m, 4H), 7.78-7.74 m, 4H) 7.36-7.32 (m, 3H), 4.62 (d, 2H), 4.23 (s, 2H), 4.01 (s, 2H). Anal. Calcd. for C ₃₉ H ₂₆ N ₄ Br ₂ (%): C, 65.93; H, 3.69; N, 7.89. Found: C, 65.74; H, 3.93; N, 7.65.

[Production Example 9]

Preparation of (8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine

 4-bromonaphthalen-1-amine (10 g, 45.03 mmol) was added to trifluoroacetic acid (100 ml) and the temperature was lowered to 0 ° C. Paraformaldehyde (2.7 g, 89.91 mmol) was added thereto and stirred for 60 hours. After removing half of the solvent under reduced pressure, ammonium hydroxide (100 ml) was added and the pH was adjusted to 14. Water (500 ml) was added and stirred for 30 minutes, followed by filtration to remove the solid. The filtered solid was recrystallized from ethanol to obtain Compound I (10.1 g, 93.0%) as a white solid.

^{1 H NMR (400 MHz, CDCl} 3): δ 7.43 - 7.41 (t, 4H), 7.19 (s, 2H), 6.95 (d, 4H), 4.63 (d, 2H), 4.26 (s, 2H), 4.08 (s, 2H). Anal. Calcd. for C ₂₃ H ₁₆ N ₂ Br ₂ , (%): C, 57.53; H, 3.36; N, 5.83. Found: C 57.14%, H 3.83%, N 6.18%.

[Production Example 10]

Preparation of (8S, 18S) -3,13-dibromo-7,17-dihydro-8,18-methanodipyreno [1,2-b: 1 ', 2'-f] [1,5] diazocine (J)

 6-bromopyren-1-amine (2.33 g, 7.87 mmol) was added to trifluoroacetic acid (30 ml) and the temperature was lowered to 0 ° C. Paraformaldehyde (0.52 g, 17.32 mmol) was added and stirred for 48 hours. After removing half of the solvent by reducing the pressure, ammonium hydroxide (60 ml) was added to adjust the pH to 14. Water (300 ml) was added and stirred for 30 minutes, followed by filtering to remove the solid. And recrystallized with ethanol to obtain a solid target compound J (2.30 g, 93.1%).

^{1 H NMR (400 MHz, CDCl} 3): δ 7.55 - 7.49 (m, 10H), 7.08 (d, 2H), 6.89 (s, 2H), 4.66 (d, 2H), 4.32 (s, 2H), 4.12 (d, 2H). Anal. Calcd. For C ₃₅ H ₂₀ N ₂ Br ₂ (%): C, 66.90; H, 3.21; N, 4.46. Found: C, 66.63; H, 3.47; N, 4.80.

[Example 1]

Preparation of 2,8-bis (4- (9H-carbazol-9-yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY22)

To a mixed solution of toluene (40 ml), ethanol (20 ml) and water (20 ml) was added 2,8-dibromo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.15 g, 0.13 mmol), 2M potassium (0.15 g, 0.13 mmol), and tetrakis (triphenylphosphine) palladium (0) (1 g, 2.63 mmol) carbonate (20 ml) was added thereto, and the mixture was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane: DCM = 5: 1 to obtain a solid product (0.99 g, 54.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 7.85 (t, 2H), 7.78 - 7.72 (m, 8H), 7.48 - 7.43 (m, 8H), 7.40 - 7.22 (m , 10H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. For C ₅₁ H ₃₆ N ₄ (%): C, 86.90; H, 5.15; N, 7.95. Found: C, 86.52; H, 5.57; N, 7.91.

[Example 2]

2,8-bis (3- (9H-carbazol-9-yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY23)

 To a mixed solution of toluene (40 ml), ethanol (20 ml) and water (20 ml) was added 2,8-dibromo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (Triphenylphosphine) palladium (0) (0.15 g, 0.13 mmol), 2M potassium (1 g, 2.63 mmol), (3- (9H- carbonate (20 ml) was added thereto, and the mixture was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane: DCM = 5: 1 to obtain a solid product (1.23 g, 66.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 7.85 (t, 2H), 7.80 - 7.74 (m, 8H), 7.48 - 7.43 (m, 8H), 7.40 - 7.22 (m , 10H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. _{For C 51 H 36 N 4 (} %): C, 86.90; H, 5.15; N, 7.95. Found: C, 86.57; H, 5.58; N, 7.85.

[Example 3]

2,8-bis (3- (10-phenylanthracen-9-yl) -9H-carbazol-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine ( KKY28)

 2,8-Dibromo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.6 g, 1.59 mmol), 3- (10-phenylanthracen- A mixture of carbazole (1.54 g, 3.66 mmol), copper powder (0.41 g, 6.36 mmol), dibenzo-18-crown-6 (0.12 g, 0.32 mmol) and potassium carbonate (1.76 g, 12.7 mmol) ml) and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane: EA = 3: 1 to obtain a solid product (0.45 g, 51%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.43 (s, 2H), 7.98 (d, 8H), 7.82 (d, 4H), 7.78 - 7.53 (m, 12H), 7.48 - 7.42 (m, 12H ), 7.40 (t, 2H), 7.32 (m, 6H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. For C ₇₉ H ₅₂ N ₄ (%): C, 89.74; H, 4.96; N, 5.30. Found: C, 89.41; H, 5.37; N, 5.22.

[Example 4]

9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1, , 5] diazocine (KKY25)

Synthesis of 3- (9H-carbazol-9-yl) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.5 g, 1.05 mmol) phenyl) -9H-carbazole (1.07 g, 2.63 mmol), copper (0.4 g, 6.3 mmol) and potassium carbonate (0.87 g, 6.3 mmol) were dissolved in DMF (15 ml) and refluxed for 72 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. The solid product (0.57 g, 51.0%) was obtained by liquid chromatography using dichloromethane as a developing solvent.

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 8.21 (t, 6H), 7.88 - 7.76 (m, 14H), 7.60 (d, 2H), 7.54 (d, 8H), 7.40 - 7.32 (m, 12H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. for C ₇₅ H ₅₀ N ₆ (%): C, 87.01; H, 4.87; N, 8.12. Found: C, 86.68; H, 5.03; N, 8.29.

[Example 5]

(5S, 11S) -2,8-bis (9-phenyl-9H-carbazol-3-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY24)

(5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] thiophene was dissolved in a mixed solution of toluene (60 ml), ethanol (30 ml) (2.00 g, 4.22 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (2.90 g, 10.10 mmol), tetrakis (triphenylphosphine) palladium mmol) and potassium carbonate (1.75 g, 12.66 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. The solid product (1.68 g, 56.6%) was obtained by column chromatography using hexane: acetone = 3: 1 as eluent.

¹ H NMR (400 MHz, CDCl ₃ ):? 8.29 (s, 2H), 7.93-7.90 (m, 4H), 7.86-7.83 m, 4H), 7.51-7.47 (m, 6H), 7.40-7.36 (m, 5H), 4.63 (d, 2H), 4.26 (s, 2H), 4.02 (s, 2H). Anal. Calcd. _{For C 51 H 36 N 4 (} %): C, 86.90; H, 5.15; N, 7.95. Found: C, 86.62; H, 5.29; N, 8.09.

[Example 6]

(5S, 11S) -2,8-di (9H-carbazol-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

To a solution of (5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (1.0 g, 2.1 mmol) in N, N-dimethylacetamide ), 9H-carbazole (1.4 g, 8.3 mmol) and Cu ₂ O (1.20 g, 8.40 mmol) were added and refluxed for 24 hours. After the reaction solution was made, the solvent was removed by decompression. After extraction with dichloromethane and washing with water, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. The remaining solid was separated by liquid chromatography using Ethylacetate: Hexane (1: 1) as eluent and brown solid product (0.85 g, 73%) was obtained.

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.10 (d, 4H), 7.40 - 7.30 (m, 12H), 7.20 (m, 4H), 7.10 (s, 2H), 4.80 (d, 2H), 4.40 (s, 2 H), 4.30 (d, 2 H). Anal. Calcd. For C ₃₉ H ₂₈ N ₄ (%): C, 84.75; H, 5.11; N, 10.14. Found: C, 84.24; H, 5.37; N, 10.39.

[Example 7]

-9'-yl) -6,12-dihydro-5,11-methanodibenzo [ b, f] [1,5] diazocine

To a solution of (5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.3 g, 0.6 mmol) in N, N-dimethylacetamide ), 9'H-9,3 ': 6', 9 "-tercarbazole (0.7 g, 1.4 mmol) and Cu ₂ O (0.34 g, 2.40 mmol) were added and refluxed for 48 hours. After the reaction solution was cooled, 100 ml of water was added to precipitate it. The red precipitate was filtered off, extracted with dichloromethane and washed with water. The organic layer was separated, dried over sodium sulfate (anhydrous), and the filtrate was evaporated under reduced pressure to remove the solvent. The remaining solid was recrystallized from dichloromethane: hexane (1: 1) to obtain a brown solid (0.48 g, 53%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8,20 (s, 4H), 8.10 (d, 8H), 7.60-7.36 ), 5.00 (d, 2H), 4.50 (s, 2H), 4.40 (d, 2H). Anal. Calcd. For C ₈₇ H ₅₆ N ₈ (%): C, 86.11; H, 4.65; N, 9.24. Found: C, 85.67; H, 4.91; N, 9.42.

[Example 8]

(5S, 11S) -2,8-bis (3- (10 - ([1,1'-biphenyl] -4-yl) anthracen-9- yl) -9H-carbazol- dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY29)

To a solution of (5S, 11S) -2,8-diiodo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.70 g, 1.48 mmol), 3- (1.54 g, 3.11 mmol) and Cu ₂ O (0.64 g, 4.50 mmol) were added to the mixture, and the mixture was stirred for 48 hours Lt; / RTI > After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane and washing with water, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Dichloromethane: Hexane (1: 3) as a developing solvent was separated by liquid chromatography and recrystallized with ethanol to obtain a solid product (0.90 g, 52.02%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.39 (s, 2H), 8.01-7.97 (m, 10H), 7.82-7.78 (m, 6H), 7.74-7.68 (m, 10H), 7.47-7.42 (m, 10H), 7.39-7.55 (m, 8H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. For C ₉₁ H ₆₀ N ₄ (%): C, 90.37; H, 5.00; N, 4.63. Found: C, 89.88; H, 5.27; N, 4.85.

[Example 9]

2,8-Bis (4- (9-phenyl-9H-carbazol-3-yl) naphthalen-1-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5]

To a mixed solution of toluene (40 ml), ethanol (20 ml) and water (20 ml) was added 2,8-bis (4-bromonaphthalen-1-yl) -6,12-dihydro-5,11-methanodibenzo [b (1.3 g, 2.06 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid (1.48 g, 5.14 mmol), tetrakis (triphenylphosphine) palladium g, 0.103 mmol) and 2M potassium carbonate (20 ml) were added, and the mixture was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane: EA = 3: 1 to obtain a solid product (1.18 g, 60.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 7.98 (d, 4H), 7.90 (d, 4H), 7.80 - 7.62 (m, 16H), 7.55 (d, 4H), (D, 2H), 7.32 (t, 4H), 7.30-7.26 (m, 6H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. For C ₇₁ H ₄₈ N ₄ (%): C, 89.09; H, 5.05; N, 5.85. Found: C, 88.76; H, 5.23; N, 6.01.

[Example 10]

2,8-Bis (4- (4- (9H-carbazol-9-yl) phenyl) naphthalen-1-yl) -6,12-dihydro-5,11-methanodibenzo [ diazocine

To a mixed solution of toluene (40 ml), ethanol (20 ml) and water (20 ml) was added 2,8-bis (4-bromonaphthalen-1-yl) -6,12-dihydro-5,11-methanodibenzo [b yl) phenyl] boronic acid (1.48 g, 5.14 mmol), tetrakis (triphenylphosphine) palladium (0) (1.30 g, 0.12 g, 0.103 mmol) and 2M potassium carbonate (20 ml) were added, and the mixture was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane: EA = 3: 1 to obtain a solid product (1.15 g, 58.0%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.45 (s, 2H), 7.98 (d, 4H), 7.90 2H), 4.60 (d, 2H), 7.50 (d, 2H), 7.50 (d, 2H) ). Anal. Calcd. For C ₇₁ H ₄₈ N ₄ (%): C, 89.09; H, 5.05; N, 5.85. Found: C, 88.67; H, 5.32; N, 6.01.

[Example 11]

2,8-bis (4- (9- (1,1'-biphenyl) -3-yl) -9H-carbazol-3- yl) naphthalen-1-yl) -6,12-dihydro- -methanodibenzo [b, f] [1,5] diazocine

To a mixed solution of toluene (40 ml), ethanol (20 ml) and water (20 ml) was added 2,8-bis (4-bromonaphthalen-1-yl) -6,12-dihydro-5,11-methanodibenzo [b (1, 1'-biphenyl-3-yl) -9H-carbazol-3-yl) boronic acid (1.43 g, 3.95 tetrakis (triphenylphosphine) palladium (0) (0.091 g, 0.079 mmol) and 2M potassium carbonate (20 ml) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane: EA = 3: 1 to obtain a solid product (1.05 g, 60.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 8.00 (d, 4H), 7.92 (d, 4H), 7.80 - 7.62 (m, 16H), 7.60 - 7.56 (m, 8H 2H), 4.20 (d, 2H), 7.50 (d, 2H), 7.50 (d, 2H). Anal. Calcd. For C ₈₃ H ₅₆ N ₄ (%): C, 89.86; H, 5.09; N, 5.05. Found: C, 89.78; H, 5.51; N, 4.71.

[Example 12]

2,8-Bis (3- (10- (naphthalen-1-yl) anthracen-9-yl) -9H-carbazol-9-yl) -6,12-dihydro- [1,5] diazocine (KKY26)

3-bromo-9H-carbazol-9-yl) -6,12-dihydro-5,11-dihydroxybenzoate was added to a mixed solution of toluene (40 ml), ethanol (20 ml) 9-yl) boronic acid (1.47 g, 5.13 mmol), tetrakis (triphenylphosphine) dihydrochloride (1.5 g, 2.05 mmol) ) palladium (0) (0.12 g, 0.103 mmol) and 2M potassium carbonate (20 ml) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Developing solvent: Hexane: CHCl ₃ = _3: 1 by liquid chromatography to obtain a solid product (1.16 g, 54.0%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.45 (s, 2H), 7.98 (d, , 7.55 (d, 4H), 7.42 (t, 4H), 7.40 (d, 2H), 7.32 (t, 4H), 7.30-7.26 ), 4.10 (d, 2H). Anal. Calcd. For C ₇₉ H ₅₂ N ₄ (%): C, 89.74; H, 4.96; N, 5.30. Found: C, 89.48; H, 5.18; N, 5.34.

[Example 13]

2,8-Bis (4- (9- (1,1'-biphenyl) -3-yl) -9H-carbazol-3- yl) naphthalen-1-yl) -6,12-dihydro- -methanodibenzo [b, f] [1,5] diazocine (KKY27)

3-bromo-9H-carbazol-9-yl) -6,12-dihydro-5,11-dihydroxybenzoate was added to a mixed solution of toluene (40 ml), ethanol (20 ml) -methanodibenzo [b, f] [1,5] diazocine (1.5 g, 2.05 mmol), (9 - ([1,1'-biphenyl] -3-yl) -9H-carbazol- 1.47 g, 5.13 mmol), tetrakis (triphenylphosphine) palladium (0) (0.12 g, 0.103 mmol) and 2M potassium carbonate (20 ml) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Developing solvent: Hexane: CHCl ₃ = _3: 1 by liquid chromatography to obtain a solid product (1.35 g, 60.0%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.45 (s, 2H), 7.97 (d, 4H), 7.86 (d, 4H), 7.88-7.82 , 7.56 (d, 4H), 7.42 (t, 4H), 7.40 (d, 2H), 7.32 (t, 4H), 7.30-7.26 ), 4.10 (d, 2H). Anal. Calcd. For C ₇₉ H ₅₂ N ₄ (%): C, 89.74; H, 4.96; N, 5.30. Found: C, 89.36; H, 5.04; N, 5.60.

[Example 14]

2,8-Bis (3 - ([1,1'-biphenyl] -4-yl) -9H-carbazol-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1 , 5] diazocine

3-bromo-9H-carbazol-9-yl) -6,12-dihydro-5,11-dihydroxybenzoate was added to a mixed solution of toluene (40 ml), ethanol (20 ml) biphenyl] -4-ylboronic acid (1.05 g, 5.28 mmol), tetrakis (triphenylphosphine) palladium (0) (1.5 g, 2.11 mmol) (0.12 g, 0.106 mmol) and 2M potassium carbonate (20 ml) were added, and the mixture was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. After recrystallization from ethanol, recrystallization with Hexane: EA = 3: 1 was repeated to obtain a solid product (1.05 g, 57.0%). ^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 8.01 (d, 2H), 7.88 (m, 8H), 7.77 - 7.50 (m, 12H), 7.46 (d, 2H), 2H), 4.40-7.36 (m, 6H), 7.32-7.27 (m, 6H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. For C ₆₃ H ₄₄ N ₄ (%): C, 88.29; H, 5.17; N, 6.54. Found: C, 87.88; H, 5.51; N, 6.61.

[Example 14]

2,8-Bis (3 - ([1,1'-biphenyl] -2-yl) -9H-carbazol-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, , 5] diazocine

3-bromo-9H-carbazol-9-yl) -6,12-dihydro-5,11-dihydroxybenzoate was added to a mixed solution of toluene (40 ml), ethanol (20 ml) (1.5 g, 2.11 mmol), [1,1'-biphenyl] -2-ylboronic acid (1.05 g, 5.28 mmol), tetrakis (triphenylphosphine) palladium (0) (0.12 g, 0.106 mmol) and 2M potassium carbonate (20 ml) were added, and the mixture was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. After recrystallization from ethanol, recrystallization with Hexane: EA = 3: 1 yielded a solid product (0.91 g, 50.4%). ^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 8.01 (d, 2H), 7.86 (m, 8H), 7.79 - 7.50 (m, 12H), 7.46 (d, 2H), 2H), 4.40-7.36 (m, 6H), 7.32-7.27 (m, 6H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. for C ₆₃ H ₄₄ N ₄ (%): C, 88.29; H, 5.17; N, 6.54. Found: C, 87.87; H, 5.43; N, 6.70.

[Example 15]

9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1, , 5] diazocine

3-bromo-9H-carbazol-9-yl) -6,12-dihydro-5,11-dihydroxybenzoate was added to a mixed solution of toluene (40 ml), ethanol (20 ml) yl) phenyl) boronic acid (1.22 g, 4.23 mmol), tetrakis (triphenylphosphine) palladium (1. (0) (0.098 g, 0.0845 mmol) and 2M potassium carbonate (20 ml) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. After recrystallization from ethanol, recrystallization with Hexane: EA = 3: 1 gave a solid product (1.00 g, 58.5%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 8.21 (t, 6H), 7.88 - 7.76 (m, 14H), 7.60 (d, 2H), 7.54 (d, 8H), 7.40 - 7.32 (m, 12H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. for C ₇₅ H ₅₀ N ₆ (%): C, 87.01; H, 4.87; N, 8.12. Found: C, 86.74; H, 5.02; N, 8.24.

[Example 16]

(5S, 11S) -2,8-bis (3- (10- (naphthalen-2-yl) anthracen-9-yl) -9H-carbazol-9- yl) -6,12-dihydro- methanodibenzo [b, f] [1,5] diazocine

 (5S, 11S) -2,8-bis (3-bromo-9H-carbazol-9-yl) -6,12-dihydroxybenzoic acid was added to a mixed solution of toluene (40 ml), ethanol (20 ml) (1.86 g, 2.67 mmol), (10- (naphthalen-2-yl) anthracen-9-yl) boronic acid (1.86 g, 5.34 mmol) tetrakis (triphenylphosphine) palladium (0) (0.16 g, 0.14 mmol) and potassium carbonate (1.11 g, 8.03 mmol) were added and refluxed for 18 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. The yellow solid product (1.62 g, 52.4%) was obtained by recrystallization from hexane: dichloromethane = 1: 1 solution.

¹ H NMR (400 MHz, CDCl ₃ ):? 8.49-8.47 (d, 4H), 8.41 (s, 2H), 7.99-7.94 (m, 10H), 7.75-7.72 2H), 4.01 (s, 2H), 4.62 (d, 2H), 4.60-7.55 (m, 2H) ). Anal. Calcd. for C ₈₇ H ₅₆ N ₄ (%): C, 90.28; H, 4.88; N, 4.84. Found: C, 89.84; H, 5.19; N, 4.97.

[Example 17]

2,8-Bis (3- (10- (naphthalen-1-yl) anthracen-9-yl) -9H-carbazol-9-yl) -6,12-dihydro- [1,5] diazocine

 3-bromo-9H-carbazol-9-yl) -6,12-dihydro-5,11-dihydroxybenzoate was added to a mixed solution of toluene (40 ml), ethanol (20 ml) 9-yl) boronic acid (1.23 g, 3.52 mmol), tetrakis (triphenylphosphine) palladium (II) ) palladium (0) (0.081 g, 0.0705 mmol) and 2M potassium carbonate (20 ml) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Ethanol, and then recrystallized with Hexane: EA = 3: 1 to obtain a solid product (1.03 g, 64.0%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.45 (s, 2H), 7.95 (d, 6H), 7.82 (d, 4H), 7.78 - 7.53 (m, 12H), 7.50 (d, 6H), 2H), 7.42-7.42 (m, 12H), 7.40 (t, 2H), 7.32 (m, 6H), 4.60 (d, 2H), 4.22 (s, 2H), 4.10 (d, 2H). Anal. Calcd. For C ₈₇ H ₅₆ N ₄ (%): C, 90.28; H, 4.88; N, 4.84. Found: C, 89.77; H, 5.23; N, 5.00.

[Example 18]

(5S, 11S) -2,8-bis (3- (pyrazin-1-yl) -9H-carbazol-9-yl) -6,12-dihydro-5,11-methanodibenzo [ 5] diazocine

 (5S, 11S) -2,8-bis (3-bromo-9H-carbazol-9-yl) -6,12- dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.93 g, 1.31 mmol), pyrene-1-ylboronic acid (0.71 g, 2.88 mmol), tetrakis (triphenylphosphine) palladium g, 0.07 mmol) and potassium carbonate (0.54 g, 3.91 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane: Dichloromethane = 1: 1 as a developing solvent and then recrystallized with EtOH aqueous solution to obtain a solid product (0.71 g, 57.3%).

^{1 H NMR (400 MHz, CDCl} 3): δ 8.41 (s, 2H), 8.01 - 7.94 (m, 7H), 7.86 - 7.83 (m, 6H), 7.77 - 7.72 (m, 5H), 7.65 - 7.59 ( m, 6H), 7.51-7.46 (m, 8H) 7.37-7.33 (m, 4H), 4.62 (d, 2H), 4.23 (s, 2H), 4.01 (s, 2H). Anal. Calcd. for C ₇₁ H ₄₄ N ₄ (%): C, 89.47; H, 4.65; N, 5.88. Found: C, 89.02; H, 4.93; N, 6.05.

[Example 19]

(8S, 16S) -5,13-bis (9-phenyl-9H-carbazol-2-yl) -7,15-dihydro-8,16-methanodinaphtho [1,2- ] [1,5] diazocine

 (8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-dione] was added to a mixed solution of toluene (40 ml), ethanol (20 ml) (9-phenyl-9H-carbazol-2-yl) boronic acid (1.31 g, 4.56 mmol), tetrakis (triphenylphosphine ) palladium (0) (0.12 g, 0.10 mmol) and potassium carbonate (0.87 g, 6.29 mmol) were added thereto and refluxed for 18 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Recrystallization from hexane: dichloromethane = 1: 1 gave a light brown solid (0.93 g, 55.7%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.14 (s, 2H), 7.87-7.85 (m, 4H), 7.77-7.74 m, 5H), 7.47-7.45 (m, 5H), 7.12-7.10 (m, 4H), 4.62 (d, 2H), 4.27 (s, 2H), 4.05 (s, 2H). Anal. Calcd. for C ₅₉ H ₄₀ N ₄ (%): C: 88.03; H, 5.01; N, 6.96. Found: C, 87.71; H, 5.46; N, 6.83.

[Example 20]

(8S, 16S) -5,13-bis (9-phenyl-9H-carbazol-3-yl) -7,15-dihydro-8,16-methanodinaphtho [1,2- ] [1,5] diazocine (KKY32)

 (8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-dione] was added to a mixed solution of toluene (60 ml), ethanol (30 ml) (9-phenyl-9H-carbazol-3-yl) boronic acid (1.38 g, 4.80 mmol), tetrakis (triphenylphosphine ) palladium (0) (0.20 g, 0.172 mmol) and potassium carbonate (1.38 g, 10.0 mmol) were added and refluxed for 24 hours. After the reaction solution was made, the solvent was removed by decompression. After extraction with dichloromethane and washing with water, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Dichloromethane: Hexane (3: 1) as a developing solvent was separated by liquid chromatography and recrystallized with ethanol to obtain a solid product (0.88 g, 52.8%).

¹ H NMR (400 MHz, CDCl ₃ ):? 7.80-7.75 (m, 4H), 7.72-7.66 (m, 6H), 7.55-7.49 2H), 7.28 (m, 4H), 6.99 (m, 4H), 4.67 (d, 2H), 4.32 (s, 2H), 4.11 Anal. Calcd. For C ₅₉ H ₄₀ N ₄ (%): C, 88.03; H, 5.01; N, 6.96. Found: C, 87.78; H, 5.37; N, 6.85.

[Example 21]

(8S, 16S) -5,13-bis (6,9-diphenyl-9H-carbazol-3-yl) -7,15-dihydro-8,16-methanodinaphtho [ -f] [1,5] diazocine

(8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-dione] was added to a mixed solution of toluene (40 ml), ethanol (20 ml) 9H-carbazol-3-yl) boronic acid (1.66 g, 4.57 mmol), tetrakis (triphenylphosphine) palladium (triphenylphosphine) palladium (0) (0.12 g, 0.10 mmol) and potassium carbonate (0.87 g, 6.29 mmol) were added and refluxed for 18 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Recrystallization from hexane: dichloromethane = 1: 1 gave a light brown solid (1.31 g, 65.6%). ^{1 H NMR (400 MHz, CDCl} 3): δ 8.41 (s, 2H), 8.01 - 7.97 (m, 6H), 7.93 - 7.89 (m, 8H), 7.85 - 7.80 (m, 8H), 7.74 - 7.72 ( m, 7H), 7.62-7.58 (m, 7H), 7.09-7.06 (m, 4H), 4.61 (d, 2H), 4.30 (s, 2H), 4.10 (s, 2H). Anal. Calcd. For C ₇₁ H ₄₈ N ₄ (%): C, 89.09; H, 5.05; N, 5.86. Found: C, 88.76; H, 5.54; N, 5.70.

[Example 22]

(8S, 16S) -5,13-bis (4- (9H-carbazol-9-yl) phenyl) -7,15-dihydro-8,16-methanodinaphtho [ f] [1,5] diazocine

(8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-dione] was added to a mixed solution of toluene (40 ml), ethanol (20 ml) 9-yl) phenyl) boronic acid (1.31 g, 4.56 mmol), tetrakis (triphenylphosphine) palladium triphenylphosphine palladium (0) (0.12 g, 0.10 mmol) and potassium carbonate (0.87 g, 6.29 mmol) were added and refluxed for 18 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. Hexane as a developing solvent was separated by liquid chromatography to obtain a light brown solid product (0.99 g, 59.3%). ^{1 H NMR (400 MHz, CDCl} 3): δ 7.91 - 7.87 (m, 4H), 7.78 - 7.73 (m, 6H), 7.70 - 7.65 (m, 7H), 7.58 - 7.53 (m, 6H), 7.47 - 2H), 7.42 (s, 2H), 7.42 (m, 4H), 7.42-7.39 (m, 3H), 7.30-7.27 (m, 4H). Anal. Calcd. for C ₅₉ H ₄₀ N ₄ (%): C, 88.03; H, 5.01; N, 6.96. Found: C, 87.68; H, 5.44; N, 6.88.

[Example 23]

(8S, 16S) -5,13-bis (3- (9H-carbazol-9-yl) phenyl) -7,15-dihydro-8,16-methanodinaphtho [ f] [1,5] diazocine (KKY31)

 (8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-dione] was added to a mixed solution of toluene (60 ml), ethanol (30 ml) 9-yl) phenyl) boronic acid (0.69 g, 2.40 mmol), tetrakis (triphenylphosphine) palladium triphenylphosphine palladium (0) (0.10 g, 0.086 mmol) and potassium carbonate (1.38 g, 10 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane and washing with water, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Dichloromethane: Hexane (2: 1) as a developing solvent was separated by liquid chromatography and recrystallized with ethanol to obtain a solid product (0.52 g, 60%).

¹ H NMR (400 MHz, CDCl ₃ ):? 7.76-7.74 (m, 4H), 7.70-7.65 (m, 6H), 7.58-7.55 2H), 4.32 (s, 2H), 4.12 (d, 2H), 7.39 (m, 6H), 7.31-7.28 . Anal. Calcd. For C ₅₉ H ₄₀ N ₄ (%): C, 88.03; H, 5.01; N, 6.96. Found: C, 87.68; H, 5.47; N, 6.85.

[Example 24]

(8S, 16S) -5,13-bis (3- (9,9'-spirobi [fluoren] -2-yl) -9H-carbazol-9-yl) -7,15- dihydro- 8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine (KKY30)

Preparation of 3- (9,9'-spirobi [fluoren] -2-yl) -9H-carbazole

 3-bromo-9H-carbazole (2.21 g, 9.0 mmol) and 9,9'-spirobi [fluoren] -7-ylboronic acid were added to a mixed solution of toluene (60 ml), ethanol (30 ml) (0.52 g, 0.45 mmol) and potassium carbonate (5.52 g, 40.0 mmol) were added to the mixture, and the mixture was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane and washing with water, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Dichloromethane: Hexane (1: 3) was isolated by liquid chromatography and recrystallized from ethanol to obtain a pale yellow solid product (2.64 g, 61.0%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.01 (d, 1H), 7.83-7.80 (m, 5H), 7.75-7.73 (m, 6H), 7.62-7.60 m, 4H), 7.19-7.17 (m, 2H). Anal. Calcd. For C ₃₇ H ₂₃ N (%): C, 92.28; H, 4.81; N, 2.91. Found: C, 91.84; H, 5.15; N, 3.01.

(8S, 16S) -5,13-bis (3- (9,9'-spirobi [fluoren] -2-yl) -9H-carbazol-9-yl) -7,15- dihydro- 8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine (KKY30)

 To a solution of (8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'- -2-yl) -9H-carbazole (1.10 g, 2.30 mmol), Cu powder (0.38 g, 5.98 mmol), 3- (9,9'-spirobi [ , dibenzo-18-crown-6 (0.11 g, 0.30 mmol) and potassium carbonate (1.63 g, 11.8 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane and washing with water, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Dichloromethane: Hexane (1: 3) as a developing solvent was separated by liquid chromatography and recrystallized from ethanol to obtain a yellow solid product (0.76 g, 57.2%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.04 (d, 2H), 7.85-7.79 (m, 12H), 7.72-7.66 (m, 10H), 7.58-7.55 (m, 8H), 7.50-7.45 m, 10H), 7.32-7.29 (m, 8H), 6.99 (m, 4H), 4.65 (d, 2H), 4.32 (s, 2H), 4.12 (d, 2H). Anal. Calcd. For C ₉₇ H ₅₉ N ₄ (%): C, 90.98; H, 4.64; N, 4.38. Found: C, 90.57; H, 4.92; N, 4.51.

[Example 25]

(8S, 18S) -3,13-bis (3- (9H-carbazol-9-yl) phenyl) -7,17-dihydro-8,18-methanodipyrrolo [ f] [1,5] diazocine

 (8S, 18S) -3,13-dibromo-7,17-dihydro-8,18-methanodipyreno [1,2-b: 1 ', 2 yl) phenyl) boronic acid (1.14 g, 3.98 mmol), tetrakis (triphenylphosphine) palladium (0) (1 g, 1.59 mmol) 0.092 g, 0.080 mmol) and potassium carbonate (0.88 g, 6.36 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromethane, the organic layer was separated and dried with sodium sulfate (anhydrous), and then the solvent was removed by decompression. After recrystallization from ethanol, recrystallization with Hexane: Ethyl Acetate = 3: 1 yielded a solid product (0.99 g, 66%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.46 (s, 2H), 7.86 (t, 2H), 7.80-7.74 (m, 10H), 7.55-7.49 (m, 12H), 7.48-7.43 , 8H), 7.08 (d, 2H), 6.89 (s, 2H), 4.66 (d, 2H), 4.32 (s, 2H), 4.11 (d, 2H). Anal. Calcd. for C ₇₁ H ₄₄ N ₄ (%): C, 89.47; H, 4.65; N, 5.88. Found: C, 89.01; H, 4.83; N, 6.16.

[Example 26] Fabrication of organic electroluminescent device using methanodiacosine derivative of the present invention

First, a transparent electrode ITO thin film obtained from a glass for an OLED was subjected to ultrasonic cleaning using trichlorethylene, acetone, ethanol, and distilled water sequentially, and then stored in isopropanol before use. After forming a 60 nm hole injection layer by depositing 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine (2-TNATA) on the ITO thin film, N, N'-bis (phenyl) benzidine (NPB) was deposited thereon to form a 15 nm hole transport layer. Then, (8-hydroxyquinolinato) aluminum (III) (Alq3) was deposited as an electron transport layer on the light emitting layer to form a hole transport layer (LiF) was deposited as an electron injection layer to a thickness of 1 nm, and Al was deposited on the electron injection layer to form a cathode having a thickness of 100 nm. Thus, an organic electroluminescence Device.

The prepared organic electroluminescent device was fabricated as follows: [ITO / 2-TNATA (60 nm) / NPB (15 nm) / host EML (35 nm) / Alq3 (20 nm) / LiF (1 nm) / Al And has a laminated structure in order from the bottom. As shown in the following Table 1, five electroluminescent devices were fabricated by applying the compound of the present invention as a novel blue luminescent material to the light emitting layer (EML) of the organic electroluminescent device described above. The device characteristics (measured at @ 10 mAcm ²⁾ ) Are shown in Table 1.

compound Volt
(V) CE
(Cd / A) PE
(lm / W) EQE
(%) CIE
(x, y) EL
Max PL
Max KKY23 12.95 0.51 0.14 0.21 (0.30, 0.49) 527 426 KKY24 5.49 0.57 0.36 0.23 (0.27, 0.42) 463 451 KKY26 7.68 2.78 1.27 1.41 (0.18, 0.33) 481 481 KKY27 8.19 3.88 1.32 1.79 (0.17, 0.27) 476 464 KKY30 11.21 1.22 0.37 0.46 (0.30, 0.54) 513 399

As shown in Table 1, the organic electroluminescent device employing the methanodiacosin derivative having a carbazole functional group as substituent on both sides of the methanodiacosine skeleton of the present invention has high luminous efficiency and excellent color purity.

In addition, the compounds of the present invention exhibited a very dark blue color in a solution state, and as shown in FIGS. 8 and 9, the EL of the device of KKY26 and KKY27 sufficiently coincided with the PL of the film state, The efficiency and color purity are remarkably improved.

Claims (10)

A methenodiacosine derivative represented by the following formula (1) or (2):
[Chemical Formula 1]

(2)

(In the formulas (1) and (2)
T is

,

or

;
L ₁ to L ₆ are independently of each other a single bond or (C 6 -C 30) arylene;
Y ₁ to Y ₄ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl,
R ₁ and R ₂ are, independently of each other, (C 6 -C 30) aryl;
The aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, nitro, (C 1 -C 30) alkyl, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl. ) The method according to claim 1,
Y ₁ to Y ₄ are independently hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl in the general formulas (1) and (2)
The aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl;
Wherein R ₁ and R ₂ are (C6-C30) aryl, the same as each other. The method according to claim 1,
Meta furnace dia terazosin derivative in Formula 2 R ₁ and R ₂ are independently a phenyl, diphenyl or naphthalenyl each other. The method according to claim 1,
(1) and (2) are represented by the following general formula (3) or (4).
(3)

[Chemical Formula 4]

(In the formulas (3) and (4)
T is

,

or

;
L ₁ to L ₆ are independently of each other a single bond or (C 6 -C 30) arylene;
Y ₁ to Y ₄ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl,
R ₁ and R ₂ are, independently of each other, (C 6 -C 30) aryl;
The aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl. 5. The method of claim 4,
L ₁ to L ₆ are independently of each other a single bond or a methanediozocine derivative represented by the following formula:

(Wherein R ₁₁ and R ₁₂ are independently hydrogen or (C 6 -C 30) aryl, o is an integer of 1 to 4, and when o is an integer of 2 or more, R ₁₁ and R ₁₂ may be the same or different from each other have.) 5. The method of claim 4,
In Formula 3, L ₁ and L ₂ , L ₃ and L _5, and L ₄ and L ₆ are each independently a single bond or (C 6 -C 30) arylene;
Y ₁ and Y ₃ and Y ₂ and Y ₄ are each independently hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl,
Wherein the aryl and heteroaryl of Y ₁ to Y ₄ may be further substituted with any one or more selected from cyano, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl. 5. The method of claim 4,
In Formula 4, L ₁ and L ₂ or L ₃ and L ₄ are each independently a single bond or (C 6 -C 30) arylene;
Y ₁ and Y ₂ are each hydrogen or (C 6 -C 30) aryl,
And R < ₁ > and R < ₂ > are identically (C6-C30) aryl. The method according to claim 1,
Wherein the methanodiacosin derivative is selected from the following compounds.

An organic electroluminescent device comprising a methanodiacosine derivative according to any one of claims 1 to 8. 10. The method of claim 9,
Wherein the methanodiacosin derivative is included in the light emitting layer of the organic electroluminescent device.

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