KR101841500B1 - Metanodiazocine derivatives having imidazole group and organic electroluminescent devices including the same - Google Patents

Abstract

The present invention relates to metanodiazocine derivatives having an imidazole functional group and an organic electroluminescent element including the same, and more particularly, to metanodiazocine derivatives having a variety of imidazole functional groups, which are new blue light emitting compounds usefully used in a light emitting layer of the organic electroluminescent element, on both sides, and an organic electroluminescent element including the same.

Description

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

The present invention relates to a metanodiacosine derivative and an organic electroluminescent device including the same, and more particularly to a 5,11-methanodialyloxy compound having an imidazole or imidazole derivative as a substituent on both sides of a methanodiacosine skeleton, 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. 2009-0084426

The present invention provides a methanedioxosin derivative having an imidazole functional group having excellent luminous efficiency, long life and high color purity, which is used 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 an imidazole functional group which can be used as a host and a dopant for blue luminescence with improved optical properties, and the novel methanodiacosin derivative of the present invention is represented by the following formula .

[Chemical Formula 1]

(1)

,

또는

이며;T is

,

or

;

L ₁ to L ₄ independently of one another are a single bond or (C 6 -C 30) arylene;

Ring A and ring B are imidazole or aromatic ring fused imidazole derivatives having di radicals;

Y ₁ to Y ₂ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

Imidazole derivatives in which the aryl and heteroaryl of Y ₁ to Y ₂ and the imidazole or aromatic fused ring of ring A and ring B are fused are cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine , (C6-C30) aryl and (C3-C30) 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 has an imidazole functional group as a substituent, and thus an organic electroluminescent device including the same is improved in electrical stability and lifetime characteristics, And exhibits excellent luminous efficiency and color purity.

1 is a diagram showing the UV absorbance and the PL intensity spectra of the compounds KKY58, KKY59 and KKY62 of the present invention,
2 is a graph showing IVL characteristics of an organic electroluminescent device manufactured using the compounds KKY57, KKY58 and KKY59 of the present invention,
3 is a graph showing the luminance efficiency-current density characteristics of the organic electroluminescent devices of the present compounds KKY57, KKY58 and KKY59,
4 is a graph showing the quantum efficiency-current density characteristics of the organic electroluminescent devices of the present compounds KKY57, KKY58 and KKY59,
5 is a graph showing the IVL characteristics of the organic electroluminescent devices of the compounds KKY62 and KKY64 of the present invention,
6 is a graph showing the luminance efficiency-current density characteristics of the organic electroluminescent devices of the present compounds KKY62 and KKY64,
7 is a graph showing the quantum efficiency-current density characteristics of the organic electroluminescent devices of the present invention compounds KKY62 and KKY64,
FIG. 8 is a graph showing the device EL and the film PL spectra of the compound KKY64 of the present invention.

The present invention provides a methanodiacosin derivative having an imidazole functional group which can be used as a dopant and a host for blue luminescence having excellent properties. The novel imidodiazocine derivative having imidazole functional group of the present invention is represented by the following formula .

[Chemical Formula 1]

(1)

,

또는

이며;T is

,

or

;

L ₁ to L ₄ independently of one another are a single bond or (C 6 -C 30) arylene;

Ring A and ring B are imidazole or aromatic ring fused imidazole derivatives having di radicals;

Y ₁ to Y ₂ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

Imidazole derivatives in which the aryl and heteroaryl of Y ₁ to Y ₂ and the imidazole or aromatic ring of ring A and ring B are fused are cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) (C6-C30) aryl and (C3-C30) heteroaryl.

The methanodiacosine derivative having an imidazole functional group of the present invention, specifically 5,11-methanodialyl [b, f] [1,5] diazocine derivative, has a central skeleton of 5,11-methanodialyl [ b, f] [1,5] diazosine and a variety of imidazole functional groups introduced into both 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 the formula 1, A rings and B rings of the present invention are imidazole derivatives having a di radical or fused aromatic rings, and may be selected from the following structural formulas.

(Wherein R _a and R _b are C6-C30) aryl or (C3-C30) heteroaryl.

In addition, the methanodiacosine derivative of the present invention may be represented by the following general formulas (2) to (4).

(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 2 to 4,

,

또는

이며;T is

,

or

;

L ₁ to L ₄ independently of one another are a single bond or (C 6 -C 30) arylene;

Y ₁ to Y ₂ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

R ₁ and R ₂ independently of one another are (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl, a and b are independently of each other an integer from 0 to 2;

The C ring and the D ring are, independently of each other, an aromatic fused ring;

Aryl and heteroaryl of R ₁ , R ₂ and Y ₁ to Y ₂ are independently selected from the group consisting of cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) Lt; / RTI > may be further substituted with any one or more selected from heteroaryl.

The various imidazole functional groups are necessarily introduced into both of the 5, 11-methanodialyl [b, f] [1,5] diazocine, which is the central skeleton of the methanodiacosin derivatives of the present invention, The organic electroluminescent device employed has improved mechanical and optical characteristics.

From the viewpoint of improving the luminous efficiency and lifespan characteristics, the rings A and B in formulas (2) to (4) of the present invention may be independently selected from the following structural formulas.

Preferably, Y ₁ and Y ₂ in the general formulas (2) to (4) according to an embodiment of the present invention are independently selected from hydrogen or the following structural formulas.

Wherein R ₁₁ to R ₁₄ are independently of each other a cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl or (C 3 -C 30) o is an integer of 0 to 5, p is an integer of 0 to 9, and when o and p are an integer of 2 or more, R ₁₁ to R ₁₄ may be mutually the same or different.)

Preferably in the above formula R ₁₁ to R ₁₂ independently are cyano, (C1-C30) alkyl, di (C1-C30) alkylamine or a (C6-C30) may be an aryl group to each other, in particular, R ₁₁ to R ₁₂ is cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert- butyl, diphenyl-amine, phenyl, naphthalenyl, pyrenyl, triphenyl alkylenyl or may phenanthrenyl renil, R ₁₁ to R ₁₂ may be, independently of one another, (C 1 -C 30) alkyl or (C 6 -C 30) aryl, specifically methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.

In terms of excellent efficiency and color purity, Y ₁ and Y ₂ in the above general formulas (2) to (4) may be independently selected from hydrogen or the following structural formulas.

Wherein R ₁₁ to R ₁₄ are independently of each other a cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl or (C 3 -C 30) o is an integer of 0 to 5, p is an integer of 0 to 9, and when o and p are an integer of 2 or more, R ₁₁ to R ₁₄ may be mutually the same or different.)

Preferably, the formulas (2) to (4) may be represented by the following formulas (5) to (10).

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(In the above formulas 5 to 10,

,

또는

이며;T is

,

or

;

L ₁ to L ₄ independently of one another are a single bond or (C 6 -C 30) arylene;

Y ₁ to Y ₂ independently of one another are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;

R ₂₁ and R ₂₄ independently from each other are (C 6 -C 30) aryl;

Aryl and heteroaryl of Y ₁ to Y ₂ are independently selected from the group consisting of cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl and (C 3 -C 30) More than one may be substituted.)

In terms of reaction efficiency and color purity, L ₁ and L ₂ and L ₃ and L ₄ in the general formulas (5) to (10) are preferably a single bond or (C 6 -C 30) arylene, Y ₁ and Y ₂ are the same or different and are hydrogen, (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl, the aryl and heteroaryl of Y ₁ to Y ₂ being cyano, (C 1 -C 30) (C 1 -C 30) alkylamine, (C 6 -C 30) aryl and (C 3 -C 30) heteroaryl, more preferably L ₁ and L ₂ or L ₃ and L ₄ Are the same single bond, phenylene, diphenylene, anthracenylene phenylene, anthracenylene naphthalenylene, naphthalenylene or naphthalenylenylene phenylene; Y ₁ and Y ₂ may be the same as each other or may be selected from the following structural formulas.

Wherein R ₁₁ to R ₁₄ are independently of each other a cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl or (C 3 -C 30) o is an integer of 0 to 5, p is an integer of 0 to 9, and when o and p are an integer of 2 or more, R ₁₁ to R ₁₄ may be mutually the same or different.)

The methanedioxane derivative represented by the above formula (6) or (8) is preferable from the viewpoint of having excellent efficiency and color purity.

Specifically, the methanodiacosin derivative of Formula 1 of the present invention may be selected from the following compounds, but is 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 methanodiacosin 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 and 2.

[Reaction Scheme 1]

[Reaction Scheme 2]

Wherein L and L 'are the same as defined for L ₁ to L _{2 in} the above formula (1), and Y is a group represented by the formula Y < ₁ > and Y < 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 [ A degree of vacuum of 10 to 10 ^-3 torr, a deposition rate of 0.01 to 100 A / sec, and a layer thickness range of 10 A to 5 mu m.

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

 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 a white solid compound H (10.1 g, 93.0%).

^{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 9]

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

 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. Recrystallization from ethanol gave the target compound I (2.30 g, 93.1%) as a solid.

^{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]

2,8-bis (4 '- (2,4,5-triphenyl-1H-imidazol-1-yl) - [1,1'-biphenyl] -4-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-bromophenyl) -6,12- dihydro-5,11-methanodibenzo [ 1,5] diazocine (0.85 g, 1.60 mmol), tetrakis (triphenylphosphine) palladium (1. (0) (0.09 g, 0.08 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 dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Recrystallization from ethanol (aq) gave a solid product (1.03 g, 60%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.80 (d, 8H), 7.63-7.61 (m, 8H), 7.54-7.48 (m, 12H), 7.44-7.41 (m, 12H), 7.40-7.34 (m, 6H), 7.27 (d, 2H), 7.20 (s, 2H), 6.89 (d, 2H), 4.62 (d, 2H), 4.23 (s, 2H), 4.01 Anal. Calcd. For C ₈₁ H ₅₈ N ₆ (%): C, 87.22; H, 5.24; N, 7.53. Found: C, 86.82; H, 5.34; N, 7.84.

[Example 2]

2,8-bis (10- (4- (2,4,5-triphenyl-1H-imidazol-1-yl) phenyl) anthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b , f] [1,5] diazocine (KKY64)

  (10-bromoanthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, l] was added to a mixed solution containing 40 ml of toluene, 20 ml of ethanol and 20 ml of water. phenyl] boronic acid (1.43 g, 3.43 mmol), tetrakis (triphenylphosphine) palladium triphenylphosphine) palladium (0) (0.08 g, 0.07 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 dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. After recrystallization from ethanol, recrystallization with Hexane: EA = 5: 1 yielded a solid product (0.97 g, 52.5%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.88 (d, 8H), 7.64-7.60 (m, 8H), 7.52-7.46 (m, 12H), 7.44-7.40 (m, 20H), 7.38-7.34 (d, 2H), 7.28 (d, 2H), 7.20 (s, 2H), 6.89 (d, 2H), 4.62 (d, 2H), 4.23 Anal. Calcd. for C ₉₇ H ₆₆ N ₆ (%): C, 88.56; H, 5.06; N, 6.39. Found: C, 88.01; H, 5.33; N, 6.66.

[Example 3]

2,8-bis (10- (4- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) anthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b , f] [1,5] diazocine (KKY59)

  B, f] [1,5] dioxane (80 ml) and water (10 ml) was added a solution of 2,8-bis (10-bromoanthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [ phenyl) boronic acid (1.61 g, 5.12 mmol), tetrakis (triphenylphosphine) palladium (0) (0.61 g, 0.12 g, 0.103 mmol) and potassium carbonate (1.13 g, 8.2 mmol) 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 dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Recrystallization from ethanol and recrystallization with Hexane: Ethyl Acetate = 3: 1 yielded a solid product (1.34 g, 62%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.86 (d, 4H), 7.70-7.60 (m, 8H), 7.56-7.50 (m, 8H), 7.42 (m, 8H), 7.40-7.36 (m 2H), 4.62 (d, 2H), 4.24 (s, 2H), 4.02 (d, 2H) (d, 2H). Anal. Calcd. for C ₈₁ H ₅₄ N ₆ (%): C, 87.54; H, 4.90; N, 7.56. Found: C, 86.97; H, 5.18; N, 7.85.

[Example 4]

Phenyl-6,12-dihydro-5,11-methanodibenzo [b, f] [1, 2, , 5] Preparation of diazocine (KKY54)

2,6-dihydrobenzo [b, f] [1,5] diazocine-2,8-diyl) dibenzaldehyde (1 g, 2.32 mmol), phenanthrene-9,10- A solution of dione (0.48 g, 2.32 mmol), aniline (0.26 g, 2.784 mmol) and ammonium acetate (1.79 g, 23.2 mmol) in glacial acetic acid (60 ml) And refluxed for 24 hours. The reaction solution was cooled, methanol (200 ml) was added, and the mixture was stirred. The solid was filtered and washed with methanol to obtain a solid product (1.69 g, 76.8%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.65 (d, 4H), 7.90 (t, 4H), 7.78-7.72 (m, 8H), 7.56-7.50 (m, 8H), 7.44-7.40 (m 2H), 7.30 (d, 2H), 7.30 (d, 2H), 7.30 (d, 2H). Anal. Calcd. For C ₆₉ H ₄₆ N ₆ (%): C, 86.40; H, 4.83; N, 8.76. Found: C, 85.89; H, 5.23; N, 8.88.

[Example 5]

1,2-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine Manufacturing

To a mixed solution of dioxane (80 ml) and water (10 ml) was added 2,8-dibromo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (1.00 g, 2.63 mmol ), Tetrakis (triphenylphosphine) palladium (0) (0.15 g, 0.132 mmol), (4- (2-phenyl- Potassium carbonate (1.45 g, 10.52 mmol) was added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane: Ethyl Acetate = 2: 1 to obtain a solid product (1.26 g, 63%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 7.86 (d, 4H), 7.68-7.60 (m, 6H), 7.55-7.50 (m, 8H), 7.40-7.36 2H), 7.20 (s, 2H), 6.88 (d, 2H), 4.62 (d, 2H), 4.24 (s, 2H), 4.01 (d, 2H). Anal. Calcd. For C ₅₃ H ₃₈ N ₆ (%): C, 83.88; H, 5.05; N, 11.07. Found: C, 83.29; H, 5.49; N, 11.22.

[Example 6]

Phenyl] -1H-phenanthro [9,10-d] imidazol-2-yl) phenyl) -6,12-dihydro -5,11-methanodibenzo [b, f] [1,5] diazocine

 (4-bromophenyl) -lH-phenanthro [9,10-d] imidazol-2-yl) phenyl) was added to a mixed solution of Dioxane (80 ml) Yl) boronic acid (0.67 g, 2.25 mmol) in anhydrous tetrahydrofuran (5 ml) , tetrakis (triphenylphosphine) palladium (0) (0.052 g, 0.045 mmol) and potassium carbonate (0.50 g, 3.6 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane: Ethyl Acetate = 2: 1 to obtain the product (0.78 g, 60%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.65 (d, 4H), 7.90 (t, 4H), 7.78-7.72 (m, 8H), 7.70-7.66 (m, 12H), 7.56-7.50 (m 2H), 7.30 (d, IH), 7.44-7.41 (m, 8H), 7.40-7.36 4.23 (s, 2 H), 4.01 (d, 2 H). Anal. Calcd. For C ₁₀₉ H ₇₀ N ₆ (%): C, 89.44; H, 4.82; N, 5.74. Found: C, 88.97; H, 5.19; N, 5.84.

[Example 7]

9-yl) phenyl) -1H-phenanthro < / RTI > [9,10-d] imidazol-2-yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

(4-bromophenyl) -1H-phenanthro [9,10-d] imidazole was added to a mixed solution containing 40 ml of toluene, 20 ml of ethanol and 20 ml of water. Yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.85 g, 0.76 mmol), (10 - 4-yl) anthracen-9-yl) boronic acid (0.71 g, 1.90 mmol), tetrakis (triphenylphosphine) palladium (0) (0.044 g, 0.038 mmol) and 2M potassium carbonate (20 ml) Respectively. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Recrystallization from Hexane: DCM = 1: 1 gave the product (0.75 g, 60%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.65 (d, 4H), 7.88 (t, 4H), 7.80-7.76 (m, 14H), 7.74-7.60 (m, 14H), 7.56-7.50 (m 2H), 6.89 (d, 2H), 4.62 (d, 2H), 7.30 (d, 2H), 7.44-7.41 (m, 8H), 7.40-7.36 , 4.23 (s, 2 H), 4.01 (d, 2 H). Anal. Calcd. For C ₁₂₁ H ₇₈ N ₆ (%): C, 89.93; H, 4.87; N, 5.20. Found: C, 89.58; H, 5.29; N, 5.13.

[Example 8]

1-yl) -1H-phenanthro [9,10-d] imidazol-2 (1 H) -yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY57)

(4-bromonaphthalen-1-yl) -1H-phenanthro [9,10-d] imidazol-2 was added to a mixed solution of dioxane (80 ml) yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (1.00 g, 0.82 mmol), (10- (naphthalen- (0.72 g, 2.05 mmol), tetrakis (triphenylphosphine) palladium (0) (0.05 g, 0.041 mmol) and potassium carbonate (0.45 g, 3.28 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. The product (0.76 g, 56%) was obtained by liquid chromatography using hexane: MC = 5: 1 as a developing solvent.

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.66 (d, 4H), 8.01-7.68 (m, 10H), 7.66 (t, 4H), 7.64-7.61 ), 7.54-7.48 (m, 12H), 7.44-7.41 (m, 12H), 7.40-7.34 (m, 8H), 7.28 4.62 (d, 2H), 4.23 (s, 2H), 4.01 (d, 2H). Anal. Calcd. For C ₁₂₅ H ₇₈ N ₆ (%): C, 90.22; H, 4.72; N, 5.05. Found: C, 89.74; H, 5.17; N, 5.09.

[Example 9]

1-yl) -1H-phenanthro [9,10-d] imidazol-2 < RTI ID = -yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY58)

(4-bromonaphthalen-1-yl) -1H-phenanthro [9,10-d] imidazol-2 was added to a mixed solution of dioxane (80 ml) -yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (1.00 g, 0.82 mmol), (10- (naphthalen- (0.72 g, 2.05 mmol), tetrakis (triphenylphosphine) palladium (0) (0.05 g, 0.041 mmol) and potassium carbonate (0.45 g, 3.28 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane: MC = 5: 1 as a developing solvent to obtain a solid product (0.68 g, 50%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.65 (d, 4H), 8.00-7.68 (m, 10H), 7.66 (t, 4H), 7.64-7.61 2H), 7.50-7.48 (m, 12H), 7.44-7.41 (m, 12H), 7.40-7. 34 (m, 8H) 4.61 (d, 2H), 4.23 (s, 2H), 4.01 (d, 2H). Anal. Calcd. For C ₁₂₅ H ₇₈ N ₆ (%): C, 90.22; H, 4.72; N, 5.05. Found: C, 89.74; H, 5.09; N, 5.17.

[Example 10]

2,8-bis (4- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] Manufacturing

To a mixed solution of toluene (40 ml), EtOH (20 ml) and water (20 ml) was added 2,8-dibromo-6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine Phenyl) boronic acid (1.5 g, 4.77 mmol), tetrakis (triphenylphosphine) palladium (0) (0.25 g, 0.216 mmol) was added to a solution of 4- (1-phenyl-1H- benzo [d] imidazol- mmol) and potassium carbonate (0.90 g, 6.51 mmol) 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 dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. The solid product (0.84 g, 51.5%) was obtained by column chromatography with hexane: acetone = 1: 1.

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.80-7.79 (d, 2H), 7.70-7.68 (m, 4H), 7.61-7.57 (m, 6H), 7.49-7.45 (m, 8H), 7.38 2H), 4.64 (d, 2H), 4.64 (d, 2H), 4.26 (s, 2H). Anal. Calcd. for C ₅₃ H ₃₈ N ₆ (%): C, 83.88; H, 5.05; N, 11.07. Found: C, 83.74; H, 5.47; N, 10.79.

[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

Dihydro-5,11-methanodibenzo [b, f] [1, 2-diiodo-6,12-diiodo-6,12-dixane / H ₂ O (8: 1) 5] diazocine (1.50 g, 3.95 mmol), tetrakis (triphenylphosphine) palladium (0. ) (0.23 g, 0.20 mmol) and potassium carbonate (1.64 g, 11.86 mmol) were added thereto and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. The solid product (2.40 g, 63.2%) was obtained by recrystallization from Hexane: acetone = 4: 1 solution.

¹ H NMR (400 MHz, CDCl ₃ ):? = 7.78-7.76 (d, 4H), 7.63-7.61 (m, 6H), 7.54-7.51 (m, 4H), 7.47-7.44 2H), 4.62 (d, 2H), 4.23 (s, 2H), 4.01 (d, 2H ). Anal. Calcd. for C ₆₉ H ₅₀ N ₆ (%): C, 86.04; H, 5.23; N, 8.73. Found: C, 85.68; H, 5.41; N, 8.91.

[Example 12]

2,8-bis (10- (4- (1,4,5-triphenyl-1H-imidazol-2-yl) phenyl) anthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b , f] [1,5] diazocine ( KKY60 )

 (10-bromoanthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] thiophene in 40 ml of toluene, 20 ml of EtOH and 20 ml of water. (1,5-triphenyl-1H-imidazol-2-yl) phenyl) boronic acid (1.13 g, 2.71 mmol), tetrakis (triphenylphosphine) palladium (0) (0.07 g, 0.06 mmol) and potassium carbonate (0.51 g, 3.69 mmol) were added thereto and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane: M.C. = 1: 1 aqueous solution to obtain a solid product (0.96 g, 64.4%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.04-8.00 (m, 4H), 7.95-7.90 (m, 12H), 7.80-7.76 (m, 4H), 7.67-7.65 (D, 2H), 4.63 (d, 2H), 7.41-7.34 (m, 14H), 7.31-7.28

2H), 4.26 (s, 2H), 4.11 (d, 2H). Anal. Calcd. for C ₉₇ H ₆₆ N ₆ (%): C, 88.56; H, 5.06; N, 6.38. Found: C, 88.23; H, 5.48; N, 6.29.

[Example 13]

(5S, 11S) -2,8-bis (2 '- (1,4,5-triphenyl-1H-imidazol-2-yl) - [1,1'-biphenyl] Preparation of dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY61)

(5S, 11S) -2,8-bis (2-bromophenyl) -6,12-dihydro-5,11-methanodibenzo [b, phenyl] boronic acid (1.6 g, 3.84 mmol), tetrakis (triphenylphosphine) palladium (II) triphenylphosphine palladium (0) (0.1 g, 0.08 mmol) and potassium carbonate (0.7 g, 5.06 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Ethanol aqueous solution to obtain a solid product (0.96 g, 51.1%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 7.82-7.80 (d, 4H), 7.74-7.71 (m, 8H), 7.65-7.62 (m, 6H), 7.56-7.53 (m, 8H), 7.49 2H), 4.61 (d, 2H), 4.23 (s, 2H), 7.91-7.44 (m, 14H), 7.40-7.38 2H), 4.08 (d, 2H). Anal. Calcd. for C ₈₁ H ₅₈ N ₆ (%): C, 87.22; H, 5.24; N, 7.54. Found: C, 86.79; H, 5.64; N, 7.57.

[Example 14]

Phenyl] -7,15-dihydro-8,16-methanodinaphtho [1,2-a] b: 1 ', 2'-f] [1,5] diazocine (KKY62)

(8S, 16S) -5,13-dibromo-7,15-dihydro-8,16-methanodinaphtho [1,2-b: 1 D] imidazol-2-yl) phenyl) boronic acid (2.16 g, 6.87 mmol) was added to a solution of tetrakis (triphenylphosphine) palladium (0) (0.18 g, 0.16 mmol) and potassium carbonate (1.30 g, 9.41 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane: M.C. = 1: 1 solution to obtain a solid product (1.91 g, 71.1%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 7.83-7.80 (m, 2H), 7.74-7.70 (m, 4H), 7.63-7.57 (m, 6H), 7.51-7.44 2H), 7.25 (s, 2H), 6.90 (d, 2H), 7.63 (d, 2H). Anal. Calcd. for C ₆₁ H ₄₂ N ₆ (%): C, 85.29; H, 4.93; N, 9.78. Found: C, 84.77; H, 5.23; N, 10.00.

[Example 15]

(5S, 11S) -2,8-bis (4- (4,5-diphenyl-1- (4- (pyren- 1- yl) phenyl) -1H- imidazol- Preparation of dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (KKY65)

(5S, 11S) -2,8-bis (4- (1- (4-bromophenyl) -4,5-diphenyl-lH- imidazol-2-yl) phenyl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine (0.95 g, 0.85 mmol), pyrene- tetrakis (triphenylphosphine) palladium (0) (0.05 g, 0.04 mmol) and potassium carbonate (0.35 g, 2.53 mmol) were added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane: M.C. = 3: 1 solution to obtain a solid product (0.61 g, 52.6%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 8.01-7.98 (m, 6H), 7.84-7.79 2H), 4.25 (s, 2H), 4.71 (d, 2H), 7.37 (m, 6H), 7.31-7.28 , 2H). Anal. Calcd. for C ₁₀₁ H ₆₆ N ₆ (%): C, 88.96; H, 4.88; N, 6.16. Found: C, 88.57; H, 5.13; N, 6.30.

[Example 16]

5,13-bis (4- (1- (4- (tert-butyl) phenyl) -4,5-diphenyl-1H-imidazol-2- yl) phenyl) -7,15- dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine

Dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine-5,13-diyl dibenzaldehyde (0.70 g, (0.79 g, 5.30 mmol) and ammonium acetate (0.82 g, 10.5 mmol) were dissolved in glacial acetic acid (60 ml) to give the title compound The dissolved solution was then refluxed for 24 hours. After the reaction solution was cooled, methanol (200 ml) was added and stirred for 30 minutes. The solid was filtered and then recrystallized from an aqueous methanol solution to obtain a solid product (1.08 g, 69.8%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 8.43 - 8.40 (m, 2H), 7.82 - 7.78 (m, 4H), 7.61 - 7.54 (m, 8H), 7.46 - 7.44 (m, 8H), 7.42 2H), 4.34 (s, 2H), 4.20 (d, 2H), 7.38 (m, 6H), 7.24-7.20 d, 2 H), 1.38 (s, 18 H). Anal. Calcd. For C ₈₅ H ₇₀ N ₆ (%): C, 86.85; H, 6.00; N, 7.15. Found: C, 86.37; H, 6.28; N, 7.35.

[Example 17]

2,8-bis (10- (4- (1- (4- (tert-butyl) phenyl) -3a, 11b-dihydro-1H-phenanthro [9,10-d] imidazol- -9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

Preparation of 4,4 '- ((6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl) bis (anthracene-10,9-diyl) dibenzaldehyde

 To a mixed solution (45 ml) of dioxane and water in an 8: 1 mixture was added 2,8-bis (10-bromoanthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] 5] diazocine (2.17 g, 3.00 mmol), tetrakis (triphenylphosphine) palladium (0) (0.17 g, 0.15 mmol), potassium carbonate (1.66 g, 12 mmol ) Was added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Again, the solution extracted with hot hexane was depressurized to remove the solvent to obtain a solid product (2.02 g, 86%).

^{1 H NMR (400 MHz, CDCl} 3): δ = 9.52 (s, 2H), 8.50 - 8.47 (m, 4H), 8.06 - 8.04 (d, 4H), 7.87 - 7.84 (m, 4H), 7.56 - 7.44 (m, 12H), 7.39-7.35 (m, 6H), 4.58 (d, 2H), 4.21 (s, 2H), 4.10 (d, 2H).

Anal. Calcd. for C ₅₇ H ₃₈ N ₂ O ₂ (%): C, 87.44; H, 4.89; N, 3.58. Found: C, 87.12; H, 5.42; N, 3.28.

2,8-bis (10- (4- (1- (4- (tert-butyl) phenyl) -3a, 11b-dihydro-1H-phenanthro [9,10-d] imidazol- -9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

4,4 '- ((6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl) bis (anthracene-10,9-diyl) dibenzaldehyde ammonium acetate (0.87 g, 11.3 mmol) was added to a solution of glacial acetic acid (0.5 g, 2.81 mmol), 4- (tert-butyl) aniline (0.84 g, 5.62 mmol) and phenanthrene- (60 ml) was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. The solid product (1.25 g, 62.8%) was obtained by column chromatography with hexane: ethylacetate = 3: 1.

^{1 H NMR (400 MHz, CDCl} 3): δ 8.57 - 8.54 (m, 4H), 8.28 - 8.20 (m, 4H), 8.04 - 7.98 (m, 4H), 7.94 - 7.84 (m, 6H) 7.78 - 7.74 (m, 8H), 7.62-7.53 (m, 14H), 7.45-7.22 (m, 10H), 7.21-7.15 , ≪ / RTI > 2H), 1.38 (s, 18H). Anal. Calcd. _{for C 105 H 78 N 6 (} %): C, 88.58; H, 5.52; N, 5.90. Found: C, 88.12; H, 5.87; N, 6.01.

[Example 18]

2,8-Bis (10- (4- (1- (9,9-dimethyl-9H-fluoren-2-yl) -3a, 11b-dihydro-1H- phenanthro [9,10- yl) phenyl anthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

4,4 '- ((6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl) bis (anthracene-10,9-diyl) dibenzaldehyde g, 1.16 mmol), phenanthrene-9,10-dione (0.48 g, 2.38 mmol), 9,9-dimethyl-9H-fluoren- ) Was dissolved in glacial acetic acid (60 ml) was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. The solid product (1.14 g, 63%) was obtained by column chromatography with hexane: dichloromethane = 3: 1.

¹ H NMR (400 MHz, CDCl ₃ ):? 8.52-8.49 (m, 4H), 8.22-8.17 (m, 4H), 8.00-7.86 (m, 10H), 7.46-7.41 (m, 10H), 7.37-7.31 (m, 8H), 7.19-7.16 , ≪ / RTI > 2H), 1.32 (s, 12H). Anal. Calcd. for C ₁₁₅ H ₇₈ N ₆ (%): C, 89.47; H, 5.09; N, 5.44. Found: C, 89.08; H, 5.45; N, 5.47.

[Example 19]

2-yl) phenyl) anthracen-9-yl) -6, 8-bis (10- (3- (1- (4- Preparation of 12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

Preparation of 3,3 '- ((6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl) bis (anthracene-10,9-diyl)) dibenzaldehyde

 To a mixed solution of Dioxane (80 ml) and water (10 ml) was added 2,8-bis (10-bromoanthracen-9-yl) -6,12-dihydro-5,11-methanodibenzo [b, f] 5] diazocine (1.74 g, 2.38 mmol), (3-formylphenyl) boronic acid (0.89 g, 5.95 mmol), tetrakis (triphenylphosphine) palladium (0) (0.14 g, 0.12 mmol) ) Was added and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane was purified by column chromatography to obtain a solid product (6.30 g, 65.4%).

¹ H NMR (400 MHz, CDCl ₃ ):? = 9.41 (s, 2H), 8.42-8.39 (m, 6H), 8.01-7.97 (m, 4H), 7.85-7.81 (m, 8H), 7.41-7.36 (m, 6H), 4.54 (d, 2H), 4.20 (s, 2H), 4.11 (d, 2H). Anal. Calcd. for C ₅₇ H ₃₈ N ₂ O ₂ (%): C, 87.44; H, 4.89; N, 3.58. Found: C, 87.03; H, 5.39; N, 3.44.

2-yl) phenyl) anthracen-9-yl) -6, 8-bis (10- (3- (1- (4- Preparation of 12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

3,3 '- ((6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl bis (anthracene-10,9-diyl) dibenzaldehyde (0.80 (0.37 g, 2.5 mmol) and ammonium acetate (0.78 g, 10 mmol) were dissolved in glacial acetic acid (80 ml) The mixed solution was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Methanol (100 ml) was added and stirred for 30 minutes, followed by filtration to obtain a solid product (0.90 g, 63%).

^{1 H NMR (400 MHz, CDCl} 3): δ 8.61 - 8.58 (m, 4H), 8.32 - 8.28 (m, 4H), 8.00 - 7.94 (m, 6H), 7.90 - 7.84 (m, 4H) 7.76 - 7.71 (m, 8H), 7.64-7.54 (m, 14H), 7.47-7.36 (m, 10H), 7.31-7.28 (m, 4H), 7.18-7.14 (s, 2 H), 4.30 (d, 2 H), 1.36 (s, 18 H).

Anal. Calcd. _{for C 105 H 82 N 6 (} %): C, 88.32; H, 5.79; N, 5.89. Found: C, 88.12; H, 5.87; N, 6.01.

[Example 20]

2, 5-diphenyl-1H-imidazol-2-yl) phenyl) anthracene-9- yl) -6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine

3,3 '- ((6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl bis (anthracene-10,9-diyl) dibenzaldehyde (1.00 (0.67 g, 3.18 mmol), 9,9-dimethyl-9H-fluoren-2-amine (0.66 g, 3.18 mmol) and ammonium acetate (0.99 g, acetic acid (80 ml) was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Methanol (100 ml) was added and stirred for 30 min. The solid precipitate was filtered and recrystallized from hexane / acetone (5: 1) to obtain a solid product (1.19 g, 60.8%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.58 - 8.52 (m, 4H), 8.30 - 8.25 (m, 4H), 8.07-7.91 (m, 8H), 7.86-7.80 (m, 8H), 7.63-7.41 (m, 16H), 7.38-7.35 (m, 8H), 7.18-7.13 , ≪ / RTI > 2H), 1.35 (s, 12H). Anal. Calcd. for C ₁₁₅ H ₈₂ N ₆ (%): C, 89.23; H, 5.34; N, 5.43. Found: C, 88.92; H, 5.71; N, 5.37.

[Example 21]

2-yl) phenyl) anthracen-9-yl) -6,12-dihydro-5,10- , 11-methanodibenzo [b, f] [1,5] diazocine

3,3 '- ((6,12-Dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl bis (anthracene-10,9-diyl) dibenzaldehyde g, 1.27 mmol), benzyl (0.67 g, 3.18 mmol), p-toluidine (0.34 g, 3.18 mmol) and ammonium acetate (0.99 g, 12., 7 mmol) in glacial acetic acid Was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Methanol (100 ml) was added and the mixture was stirred for 30 minutes. After filtration, the solid precipitate was recrystallized from hexane / acetone (5: 1) to obtain solid product (1.08 g, 63.2%).

^{1 H NMR (400 MHz, CDCl} 3): δ 8.41 - 8.38 (m, 6H), 7.96 - 7.92 (m, 6H), 7.86 - 7.78 (m, 12H), 7.71 - 7.66 (m, 8H), 7.61 - 2H), 4.41 (d, 2H), 1.36 (s, 2H), 7.51 (m, 10H), 7.39-7.31 (m, 12H), 7.18-7.14 6H). Anal. Calcd. for C ₉₉ H ₇₀ N ₆ (%): C, 88.49; H, 5.25; N, 6.26. Found: C, 88.12; H, 5.71; N, 6.17.

[Example 22]

4,4 '- (2,2' - (((6,12-dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl) bis (anthracene- bis (3,1-phenylene)) bis (4,5-diphenyl-1H-imidazole-2,1-diyl) dibenzonitrile

3,3 '- ((6,12-Dihydro-5,11-methanodibenzo [b, f] [1,5] diazocine-2,8-diyl bis (anthracene-10,9-diyl) dibenzaldehyde (0.67 g, 3.18 mmol), 4-aminobenzonitrile (0.38 g, 3.18 mmol) and ammonium acetate (0.99 g, 12., 7 mmol) were dissolved in glacial acetic acid Was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Methanol (100 ml) was added and stirred for 30 min. The solid precipitate was filtered and recrystallized from hexane / acetone (5: 1) to obtain solid product (1.17 g, 67.6%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.34 (d, 4H), 7.88-7.84 (m, 14H), 7.70-7.69 m, 12H), 7.19-7.15 (m, 8H), 7.05-6.96 (m, 4H), 5.50 (d, 2H), 5.30 (s, 2H), 5.07 (d, 2H). Anal. Calcd. for C ₉₉ H ₆₄ N ₈ (%): C, 87.07; H, 4.72; N, 8.21. Found: C, 86.83; H, 5.11; N, 8.06.

[Example 23]

4,4 '- (2,2'- ((7,15-dihydro-8,16-methanodinaphtho [1,2-b: 1', 2'-f] [1,5] diazocine- bis (4,1-phenylene) bis (1H-phenanthro [9,10-d] imidazole-2,1-diyl) dibenzonitrile

Dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine-5,13-diyl dibenzaldehyde (1.00 g, 1.89 mmol), phenanthrene-9,10-dione (0.78 g, 3.70 mmol), 4-aminobenzonitrile (0.89 g, 7.50 mmol) and ammonium acetate (1.16 g, 15.1 mmol) were dissolved in glacial acetic acid The solution was refluxed for 24 hours. The reaction solution was cooled, water (300 ml) was added thereto, and the mixture was stirred for 30 minutes. The precipitate was filtered and recrystallized from an aqueous ethanol solution to obtain a solid product (1.40 g, 66.7%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.46-8.42 (m, 4H), 7.99-7.94 (m, 4H), 7.84-7.76 2H), 4.63 (d, 2H), 7.35 (m, 12H), 6.98-6.94 (m, 4H). Anal. Calcd. For C ₇₉ H ₄₈ N ₈ (%): C, 85.54; H, 4.36; N, 10.10. Found: C, 85.12; H, 4.73; N, 10.15.

[Example 24]

5,13-bis (4- (1- (p-tolyl) -1H-phenanthro [9,10-d] imidazol-2-yl) phenyl) -7,15- dihydro-8,16-methanodinaphtho [ 2-b: Preparation of 1 ', 2'-f] [1,5] diazocine

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

Dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine-5,13-diyl dibenzaldehyde (1.00 g, (0.81 g, 7.60 mmol) and ammonium acetate (1.17 g, 15.2 mmol) were dissolved in glacial acetic acid (60 ml) and mixed with phenanthrene-9,10-dione The solution was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed under reduced pressure. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Ethanol aqueous solution to obtain a solid product (1.20 g, 58.5%).

^{1 H NMR (400 MHz, CDCl} 3): δ 8.43 - 8.39 (m, 4H), 7.97 - 7.93 (m, 4H), 7.83 - 7.78 (m, 6H), 7.70 - 7.67 (m, 6H), 7.60 - 4H), 4.80 (d, 2H), 4.62 (s, 2H), 4.39 (m, 2H) d, 2 H), 1.36 (s, 6 H). Anal. Calcd. For C ₇₉ H ₄₈ N ₈ (%): C, 87.26; H, 5.01; N, 7.73. Found: C, 86.89; H, 5.42; N, 7.69.

[Example 25]

5,13-bis (4- (1- (4- (phenanthren-9-yl) phenyl) -1H-phenanthro [9,10-d] imidazol- , 16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine

5,13-bis (4- (1- (4-bromophenyl) -1H-phenanthro [9,10-d] imidazol-2-yl) phenyl) 2-b: 1 ', 2'-f] [1,5] diazocine

4,4 '- (7,15-Dihydro-8,16-methanodinaphtho [1,2-b: 1', 2'-f] [1,5] diazocine-5,13-diyl) dibenzaldehyde (8.00 g, 15.1 mmol), phenanthrene-9,10-dione (6.25 g, 30 mmol), 4-bromoaniline (10.3 g, 59.9 mmol) and ammonium acetate (9.25 g, 120 mmol) were dissolved in glacial acetic acid Solution. And refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed under reduced pressure. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Ethanol aqueous solution to obtain a solid product (10.5 g, 56.1%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.40-8.35 (m, 4H), 7.94-7.83 (m, 8H), 7.79-7.77 4H), 4.81 (d, 2H), 4.63 (s, 2H), 4.42 (m, 2H) d, 2H). Anal. Calcd. for C ₇₇ H ₄₈ Br ₂ N ₄ (%): C, 75.98; H, 3.98; N, 6.91. Found: C, 75.39; H, 4.32; N, 7.24.

5,13-bis (4- (1- (4- (phenanthren-9-yl) phenyl) -1H-phenanthro [9,10-d] imidazol- , 16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine

(4-bromophenyl) -1H-phenanthro [9,10-d] imidazol-2-one was added to a mixed solution of toluene (40 ml), EtOH (20 ml) yl] phenyl) -7,15-dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine (1.00 g, 0.80 mmol), phenanthren- tetrakis (triphenylphosphine) palladium (0) (0.05 g, 0.04 mmol) and potassium carbonate (0.34 g, 2.46 mmol) were added thereto and refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Hexane: M.C. = 3: 1 solution to obtain a solid product (0.62 g, 54.9%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.89 - 8.87 (m, 3H), 8.80-8.78 (m, 3H), 8.73-8.71 (m, 4H), 8.45-8.43 4H), 4.98 (d, 2H), 4.68 (m, 2H), 7.86-7.86 (m, (s, 2 H), 4.46 (d, 2 H). Anal. Calcd. _{for C 105 H 66 N 6 (} %): C, 89.34; H, 4.71; N, 5.95. Found: C, 88.79; H, 4.94; N, 6.27.

[Example 26]

5,13-bis (4- (1- (4'- (9H-carbazol-9-yl) - [1,1'-biphenyl] -4-yl) -1H-phenanthro [9,10- -2-yl) phenyl) -7,15-dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine

(4-bromophenyl) -1H-phenanthro [9,10-d] imidazol-2-one was added to a mixed solution of toluene (100 ml), EtOH (50 m) 2, 1'-dihydro-8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine (1.00 g, 0.80 mmol) (0.05 g, 0.04 mmol) and potassium carbonate (0.34 g, 2.46 mmol) were added to the mixture, and the mixture was stirred for 24 hours Lt; / RTI > After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Recrystallization from hexane solution gave a solid product (0.68 g, 55.3%).

^{1 H NMR (400 MHz, CDCl} 3): δ 8.64 - 8.60 (d, 4H), 8.41 - 8.35 (m, 8H), 8.11 - 8.06 (m, 4H), 8.00 - 7.96 (m, 4H), 7.90 - (M, 4H), 7.87 (m, 8H), 7.81-7.76 (m, 10H), 7.68-7.58 , 4.81 (d, 2H), 4.63 (s, 2H), 4.41 (d, 2H). Anal. Calcd. _{for C 105 H 66 N 6 (} %): C, 88.02; H, 4.71; N, 7.27; Found: C, 87.66; H, 4.93; N, 7.41.

[Example 27]

5,13-bis (4- (1- (9,9-dimethyl-9H-fluoren-2-yl) -4,5-diphenyl-1H- imidazol- Preparation of 8,16-methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine

4,4 '- (7,15-Dihydro-8,16-methanodinaphtho [1,2-b: 1', 2'-f] [1,5] diazocine-5,13-diyl) dibenzaldehyde (0.70 g, Ammonium acetate (0.82 g, 10.6 mmol) was added to a solution of glacial acetic acid (100 mL, 1.32 mmol), benzyl (0.56 g, 2.64 mmol), 9,9-dimethyl-9H- ) Was refluxed for 24 hours. After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Methanol (100 ml) was added and the mixture was stirred for 30 minutes. After filtration, the solid precipitate was recrystallized from hexane solution to obtain a solid product (0.91 g, 53.2%).

^{1 H NMR (400 MHz, CDCl} 3): δ 8.64 - 8.60 (d, 4H), 8.41 - 8.35 (m, 8H), 8.11 - 8.06 (m, 4H), 8.00 - 7.96 (m, 4H), 7.90 - (M, 4H), 7.87 (m, 8H), 7.81-7.76 (m, 10H), 7.68-7.58 , 4.81 (d, 2H), 4.63 (s, 2H), 4.41 (d, 2H). Anal. Calcd. for C ₉₅ H ₇₀ N ₆ (%): C, 88.07; H, 5.45; N, 6.49. Found: C, 87.63; H, 5.78; N, 6.59.

[Example 28]

5,13-bis (4- (4,5-diphenyl-1- (4- (triphenylen-2-yl) phenyl) -1H-imidazol- -methanodinaphtho [1,2-b: 1 ', 2'-f] [1,5] diazocine

To a solution of 5,13-bis (4- (1- (4-bromophenyl) -4,5-diphenyl-1H-imidazol-2-yl) phenyl) -7,15- dihydro- (1.15 g, 0.94 mmol) and triphenylen-2-ylboronic acid (0.56 g, 2.07 mmol) were added to the solution, and the mixture was refluxed for 24 hours . After the reaction solution was cooled, the solvent was removed by decompression. After extraction with dichloromathane, the organic layer was separated, dried with sodium sulfate (anhydrous), and then decompressed to remove the solvent. Recrystallization from hexane gave a solid product (0.78 g, 54.9%).

¹ H NMR (400 MHz, CDCl ₃ ):? 8.66 (m, 4H), 8.45-8.43 (m, 4H), 7.82-7.77 (m, 8H), 7.73-7.51 (m, 4H), 4.95 (d, 2H), 4.68 (m, 4H), 7.39-7.29 , ≪ / RTI > 2H), 4.43 (d, 2H). Anal. Calcd. for C ₁₁₃ H ₆₄ N ₆ (%): C, 89.53; H, 4.92; N, 5.55. Found: C, 89.17; H, 5.21; N, 5.62.

[Example 29] Fabrication of an organic electroluminescent device using the 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
(Im / W) EQE
(%) CIE
(x, y) EL
_Max PL
_Max KKY57 8.53 4.29 1.85 2.61 (0.17, 0.25) 472 415, 436 KKY58 7.85 1.61 0.68 0.68 (0.25, 0.43) 496 434 KKY59 8.41 1.16 0.38 0.57 (0.22, 0.33) 518 484 KKY62 8.78 0.58 0.23 0.52 (0.17, 0.15) 453 428 KKY64 8.66 2.84 1.17 2.21 (0.15, 0.18) 467 462

As shown in Table 1, the organic electroluminescent device employing the methanodiacosin derivative having various imidazole functional groups on both sides of the metanodiacein center skeleton of the present invention has high luminous efficiency and excellent color purity.

In addition, as shown in FIG. 8, the EL of the device of the KKY64 is sufficiently in conformity with the PL of the film state so that the quantum efficiency and color purity as well as the luminance of the device are remarkable As shown in FIG.

Claims (10)

A metanodiacosine derivative represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

(1)
T is

,

or

;
L ₁ to L ₄ independently of one another are a single bond or (C 6 -C 30) arylene;
Ring A and ring B are imidazole or aromatic ring fused imidazole derivatives having di radicals;
Y ₁ to Y ₂ independently of one another are (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;
Imidazole derivatives in which the aryl and heteroaryl of Y ₁ to Y ₂ and the imidazole or aromatic ring of ring A and ring B are fused are cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) (C6-C30) aryl and (C3-C30) heteroaryl. The method according to claim 1,
(1) is represented by any one of the following formulas (2) to (4):
(2)

(3)

[Chemical Formula 4]

(In the above Chemical Formulas 2 to 4,
T is

,

or

;
L ₁ to L ₄ independently of one another are a single bond or (C 6 -C 30) arylene;
Y ₁ to Y ₂ independently of one another are (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;
R ₁ and R ₂ independently of one another are (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl, a and b are independently of each other an integer from 0 to 2;
C ring and D ring are aromatic fused rings;
Aryl and heteroaryl of R ₁ , R ₂ and Y ₁ to Y ₂ are independently selected from the group consisting of cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) Lt; / RTI > may be further substituted with any one or more selected from heteroaryl. 3. The method of claim 2,
Wherein the C ring and D ring in the general formulas (2) to (4) are independently selected from the following structural formulas.

The method of claim 3,
Wherein Y ₁ and Y ₂ in the general formulas (2) to (4) are independently selected from the following structural formulas.

Wherein R ₁₁ to R ₁₄ are independently of each other a cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl or (C 3 -C 30) o is an integer of 0 to 5, p is an integer of 0 to 9, and when o and p are an integer of 2 or more, R ₁₁ to R ₁₄ may be mutually the same or different.) The method of claim 3,
(2) to (4) are represented by any one selected from the following formulas (5) to (10).
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(In the above formulas 5 to 10,
T is

,

or

;
L ₁ to L ₄ independently of one another are a single bond or (C 6 -C 30) arylene;
Y ₁ to Y ₂ independently of one another are (C 6 -C 30) aryl or (C 3 -C 30) heteroaryl;
R ₂₁ and R ₂₄ independently from each other are (C 6 -C 30) aryl;
Aryl and heteroaryl of Y ₁ to Y ₂ are independently selected from the group consisting of cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl and (C 3 -C 30) More than one may be substituted.) 6. The method of claim 5,
In the general formulas (5) to (10), L ₁ , L ₂ and L ₃ are each independently a single bond or (C 6 -C 30) arylene;
Y ₁ and Y ₂ are (C6-C30) aryl or (C3-C30) heteroaryl,
Wherein the aryl and heteroaryl of Y ₁ to Y ₂ is selected from the group consisting of cyano, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl and (C 3 -C 30) Wherein the methanedioxacin derivative is further substituted with a methanedithiocin derivative. 6. The method of claim 5,
In formulas (5) to (10), L ₁ and L _2, or L ₃ and L ₄ are each independently a single bond, phenylene, diphenylene, anthracenylene phenylene, anthracenylene naphthalenylene naphthalene or naphthalene Nylene phenylene;
Y ₁ and Y ₂ are the same as each other and are selected from the following structural formulas.

Wherein R ₁₁ to R ₁₄ are independently of each other a cyano, nitro, (C 1 -C 30) alkyl, di (C 1 -C 30) alkylamine, (C 6 -C 30) aryl or (C 3 -C 30) o is an integer of 0 to 5, p is an integer of 0 to 9, and when o and p are an integer of 2 or more, R ₁₁ to R ₁₄ may be mutually the same or different.) 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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