WO2022045325A1 - Carbazole compound, and functional material and light emitting element that include same - Google Patents

Abstract

An indolo[3,2,1-jk]carbazole compound according to one aspect of the present invention is represented by formula (1). (In this general formula, R₁, R₂, R₃, and R₄ each independently represent a hydrogen atom, a C1-12 alkyl group, a phenyl group, a cyano group, a polycyclic aromatic hydrocarbon group, or a hetero aromatic ring group. Additionally, in this formula, X₁, X₂, and X₃ each independently represent a nitrogen atom or a hydrogen substituted carbon atom, but at least one of X₁, X₂, and X₃ is a nitrogen atom.)

Description

Carbazole compounds, as well as functional materials and light emitting devices containing them.

The present invention relates to a carbazole compound, a functional material containing the carbazole compound, and a light emitting device.

Organic functional materials with luminescent properties are used for various purposes such as probes and luminescent materials for organic EL, and energetically research is being conducted on the control of their physical properties. In recent years, materials having special functions such as thermally activated delayed fluorescence, room temperature phosphorescence, and polarized light emission, and materials using them have been found, and attention is being paid to future application development.

As an example of the above technique, for example, as described in Non-Patent Document 1 below, an organic light emitting material using thermally activated delayed fluorescence (hereinafter referred to as “TADF”) (hereinafter referred to as “TADF material”). ”) Is designed to have a small excited energy difference ( _ΔEST ) between single and triple terms, and thermal energy causes inverse crossing from triple term exciter to single term exciter. As a result, it is possible to realize an internal quantum efficiency of up to 100%, which is comparable to a phosphorescent material even though it is a fluorescent material. Further, since this material does not require a rare metal, it has an advantage that it is cheaper than a phosphorescent material.

Further, as an example of another technique, for example, as described in Patent Document 1, by appropriately designing an intramolecular interaction, vibration deactivation is suppressed in a solid, and long-lived phosphorescence and delayed fluorescence are suppressed. Organic phosphorescent materials that emit light have been developed, and are expected to replace conventional inorganic phosphorescent materials that have a large environmental load.

Further, as described in Patent Document 2, for example, a film having polarized light emitting characteristics has been developed by dispersing and stretching a light emitting material having a molecular skeleton having a high aspect ratio in a polymer, and a transparent LCD. It is expected to be applied to such applications.

Japanese Unexamined Patent Publication No. 2017-149888 International Publication WO 2019/0222111 International Publication WO 2014/024856

By the way, the performance of a device using a TADF material strongly depends on the host material in which the light emitting material is dispersed. For example, although the host material is reported in Patent Document 3, the performance remains in the same range as the conventional material, and the host material that is sufficiently optimized has not yet been found. ..

In addition, although many light emitting materials have been found so far, including the above prior art documents, the development of deep blue and high color purity light emitting materials required for high color gamut displays and high color rendering light sources is stable. There are many sexual problems and restrictions on molecular design, and it is significantly delayed compared to other colors.

Furthermore, most organic phosphorescent materials exhibit phosphorescent properties only in the crystalline state, so there is a problem that their uses are limited. Also, few have a practical emission life in seconds. Therefore, when compared with existing inorganic phosphorescent materials, the current situation is that there is no advantage other than low environmental load.

Further, regarding the polarized light emitting material, a rigid skeleton having a high aspect ratio is required, but since the band gap is inevitably narrowed due to the extension of the conjugated length, the polarized light having deep blue and high color purity light emitting characteristics is provided. There is a problem that it is difficult to develop a light emitting material.

Therefore, in view of the above problems, it is an object of the present invention to provide a novel and useful carbazole compound, a functional material containing the same, and a light emitting device.

As a result of repeated studies to solve the above problems, the present inventors have found that a structure containing indro [3,2,1-jk] carbazole and a π-electron deficient nitrogen-containing heteroaromatic ring in one molecule is described above. We found that it would be a material to solve the problem.

That is, the indro [3,2,1-jk] carbazole compound according to one aspect of the present invention is represented by the following formula (1).

In the above general formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, polycyclic aromatic hydrocarbon groups, or Represents a heteroaromatic ring group. Further, in the above formula, X ₁ , X ₂ , and X ₃ independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ is a nitrogen atom.

Further, the indro [3,2,1-jk] carbazole compound according to another aspect of the present invention is represented by the following formula (2).

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, polycyclic aromatic hydrocarbon groups, or hetero. Represents an aromatic ring group. Further, in the above formula, X ₁ , X ₂ , and X ₃ independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ is a nitrogen atom.

Further, the functional materials according to another aspect of the present invention include the indro [3,2,1-jk] carbazole compound represented by the above formula (1) and the indro [3, represented by the above formula (2). 2,1-jk] Containing at least one of the carbazole compounds.

From this point of view, the functional material is not limited, but is preferably at least one of a light emitting material and a host material.

Further, the light emitting element according to another viewpoint of this viewpoint includes the above-mentioned functional material.

Further, the polymer composite material according to another aspect of the present invention includes an indro [3,2,1-jk] carbazole compound represented by the above formula (1) and an indro [3] represented by the above formula (2). , 2,1-jk] Containing at least one of the carbazole compounds.

Further, the functional material according to another aspect of the present invention includes the above-mentioned polymer composite material.

Further, from this viewpoint, the functional material is preferably at least one of a phosphorescent material and a polarized light emitting material, although it is not limited.

Further, a method for producing a polymer composite material according to another aspect of the present invention is represented by the indro [3,2,1-jk] carbazole compound represented by the following formula (1) and the following formula (2). It comprises a step of dispersing at least one of the indro [3,2,1-jk] carbazole compounds in a polymer heated above the glass transition temperature.

In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, polycyclic aromatic hydrocarbon groups, or Represents a heteroaromatic ring group. Further, in the above formula, X ₁ , X ₂ , and X ₃ independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ is a nitrogen atom.

As described above, the present invention makes it possible to provide a novel and useful carbazole compound, a functional material containing the same, and a light emitting device. The more specific effects of the present invention are as follows.

The carbazole compound according to the present invention (hereinafter referred to as "the present compound") can be used as a host material for an organic EL element, particularly as a host material for a TADF material. By using this compound, an organic EL device with a low drive voltage and a long life can be obtained while maintaining quantum efficiency with an appropriate energy structure, good carrier balance derived from a bipolar structure, and a highly stable structure. be able to.

In addition, this compound can be used as a light emitting material for organic EL devices. By using this compound, it is possible to realize deep blue and high color purity emission derived from a wide bandgap and a rigid structure.

In addition, by dispersing this compound in a polymer to form a polymer composite material, vibration deactivation can be suppressed by the interaction between the rigid skeleton and the polymer chain, and room temperature phosphorescence characteristics with a long life can be exhibited. Since it is transparent and can be molded arbitrarily, it can be used for various purposes as a pure organic phosphorescent material having a small environmental load.

Since the compound of the present invention has a rigid structure, a high aspect ratio, and a transition moment parallel to the major axis direction, the molecular major axis is easily oriented in the stretching direction by stretching after dispersing in the polymer. It is possible to use a polarized light emitting material having a deep blue color and high color purity.

It is a figure which shows the device characteristic when the compound prepared in an Example is used as a host material. It is a figure which shows the fluorescence spectrum of the compound produced in an Example. It is a figure which shows the phosphorescent state of the polymer composite material produced in an Example. It is a photographic figure in the light emission of the film produced in an Example. It is a figure which shows the spectrum of the polarized light emission which concerns on Example.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many embodiments, and is not limited to the embodiments and specific examples described below.

(Carbazole compound)
The first indro [3,2,1-jk] carbazole compound according to the present embodiment is represented by the following formula (1).

In the above formula (1), R ₁ , R ₂ , R ₃ , and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, and polycyclic aromatic hydrocarbon groups, respectively. , Or a heteroaromatic ring group. Further, in the above formula, X ₁ , X ₂ , and X ₃ independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ is a nitrogen atom.

Further, in the above, the polycyclic aromatic hydrocarbon group is not limited, but is preferably a polycyclic aromatic hydrocarbon group having 9 to 20 carbon atoms, for example, a pentarenyl group, an indenyl group, and the like. Carbon-condensed dicyclic system such as azulenyl group and naphthyl group, carbon-fused tricyclic system such as indacenyl group, biphenylenyl group, acenaftylenyl group, fluorenyl group, phenylenyl group, phenanthryl group and anthracenyl group, carbon condensation of pyrenyl group, chrysenyl group and the like. A hydrocarbon-condensed pentacyclic system such as a tetracyclic group, a perylenel group, a pentaphenyl group, or a pentasenyl group is preferable.

Further, in the above, examples of the heterocyclic group include a 5-membered ring, a 6-membered heterocyclic substituent, and a fused ring thereof, and examples thereof include an imidazolyl group, an oxazolyl group, and an oxadiazolyl group. , Triazolyl group, pyridyl group, pyrimidinyl group, pyrazil group, pyridadinyl group, benzimidazolyl group, imidazolyl pyridyl group, imidazolyl pyrimidinyl group, dibenzothiophenyl group, dibenzofuranyl group, quinolyl group, quinoxalyl group and the like are preferable. In addition, these may further have a substituent.

Further, as a specific example of the above, for example, the following can be given. However, this is just an example.

Further, another indro [3,2,1-jk] carbazole compound according to the present embodiment is represented by the following formula (2).

In the above formula (2), R ₁ , R ₂ , R ₃ , and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, and polycyclic aromatic hydrocarbon groups, respectively. , Or a heteroaromatic ring group. Further, in the above formula, X ₁ , X ₂ , and X ₃ independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ is a nitrogen atom. The polycyclic aromatic hydrocarbon group and the heteroaromatic ring group are the same as those in the above formula (1).

Further, as a specific example of the above, for example, the following can be mentioned. However, this is just an example.

In each of the compounds represented by the above formulas (1) and (2) (hereinafter collectively referred to as "the present compound"), all aromatic units are bonded via sp2 carbon-carbon bonds. Therefore, it is extremely stable. In addition, it has a high glass transition temperature due to the planar and rigid skeleton of this compound. Therefore, it is suitable as a thin film electronic device material.

Further, since this compound has a very deep HOMO derived from indro [3,2,1-jk] carbazole and a high triplet excitation energy, it has an energy structure suitable for a TADF material as a host material. Furthermore, since it has a bipolar structure having an indro [3,2,1-jk] carbazole which is a hole transport unit and a heterocycle which is an electron transport unit in the molecule, it has a high efficiency and low voltage drive due to a good carrier balance. And long life can be realized.

Further, since the compounds represented by the above formulas (1) and (2) both have a wide band gap and vibration is suppressed by the rigid structure, deep blue high color purity emission can be realized. That is, this compound can be used as a light emitting material.

As is clear from the above description, any of the compounds represented by the above formulas (1) and (2) can be used as a functional material, and specifically, they should be used as a light emitting material and a host material. It is possible to make a light emitting element by including this functional material. That is, it can be used as a functional material by containing at least one of the compounds represented by the above formulas (1) and (2), and a light emitting device can be realized by including this functional material. It is possible.

Further, the compounds represented by the above formulas (1) and (2) can be made into a polymer composite material by dispersing them in a polymer, and further different effects can be obtained. That is, the polymer composite material according to the present embodiment (hereinafter referred to as "the present composite material") contains at least one of the compounds represented by the above formulas (1) and (2), and this is a novel function. It can also be a sex material.

This composite material functions as a phosphorescent material that emits phosphorescence with a long life by effectively suppressing the non-radiative deactivation of triplet excitons by the interaction between the rigid skeleton and the polymer chain.

Further, as is clear from the above formulas (1) and (2), the present compound of the present composite material has a high aspect ratio, and therefore, by stretching the dispersed resin, the molecules are oriented along the polymer chain. do. Since the transition moment of this compound is parallel to the major axis due to the donor / acceptor structure, the light emission is polarized in the stretching direction, and a deep blue, high color purity polarized light emitting material can be easily obtained.

That is, this polymer composite material can exert its effect at least as a functional material for phosphorescent material use and polarized light emitting material use.

(Light emitting element)
As described above, this compound can be suitably used for a light emitting device as a functional material for an electronic device. The light emitting element is an electronic device including a cathode and an anode and a light emitting layer interposed between the electrodes, and examples of the light emitting element include an organic EL element. In an organic EL element, holes are injected from the anode and electrons are injected into the light emitting layer from the cathode, and they recombine in the light emitting layer to generate excitons, which emit light when deactivated. This organic EL element can be applied to a light source, a lighting device, a display device, and the like. The cathode, anode, and other materials constituting the light emitting layer of the organic EL element can be appropriately selected from known materials and used.

Further, the light emitting device may be provided with an electron transport layer containing an electron transport material between the cathode and the light emitting layer, and may be provided with a hole transport layer containing a hole transport material between the anode and the light emitting layer. You may. As these electron transporting materials and hole transporting materials, known materials can be appropriately used.

The material for an electronic device of the present invention can be suitably used as a host material contained in a light emitting layer. The host material is a compound that is not a light emitting material in a light emitting layer composed of two or more kinds of compounds and has the highest mixing ratio (mass ratio) in the light emitting layer. For example, the light emitting layer is If it is composed of two types of compound A and compound B and the mixing ratio thereof is A: B = 10: 90, it can be said that compound B is the host compound. Further, if the light emitting layer is composed of three types of compound A, compound B, and compound C and the mixing ratio thereof is A: B: C = 5: 10: 85, it can be said that compound C is the host compound. In the case of the two types, when A and B are the same amount, and when A: B = 1: 1, the side that is not the light emitting material is the host material.

(Method for manufacturing compounds)
By the way, the compounds represented by the general formulas (1) and (2) can be produced by a combination of known methods. Specifically, it is as follows.

First, the indro [3,2,1-jk] carbazole derivative is prepared by diazotizing the 2-aminophenylcarbazole derivative and thermally decomposing it as shown in the following reaction formula (I), as in the following reaction formula (II). A method of thermally decomposing the 2-nitrophenylcarbazole derivative under reduced pressure through a red-heated copper tube (Flash Vacuum Pyrolysis, FVP), a molecule using a palladium catalyst as shown in the following reaction formula (III). It can be produced mainly by three methods using inner CC bond formation or the like.

Further, the 2,5,11-position can be halogenated by reacting the above indro [3,2,1-jk] carbazole derivative with a halogenating agent such as NBS (see the following formula (IV)). ). In cases other than the above (III), halogen can be introduced before the formation of the indro [3,2,1-jk] carbazole ring (see (V) below).

Further, by reacting the above-mentioned obtained compound with a boric acid ester after a boric acid reaction or a lithiolation reaction, it can be induced to boronic acid or its esters (see the following formulas (VI) and (VII). ).

Further, a nitrogen-containing heteroaromatic ring unit having a halogen produced by these and a known method can be bonded by a Suzuki-Miyaura cross-coupling reaction to obtain a compound represented by the above formula (1) or (2). Yes (see formulas (VIII) and (IX) below). When the nitrogen-containing heteroaromatic ring unit side is boronic acid or an ester thereof, an equivalent compound can be obtained by using a halide of an indro [3,2,1-jk] carbazole derivative.

(Manufacturing method of polymer composite material)
Further, as described above, the polymer composite material is a polymer obtained by heating at least one of the indro [3,2,1-jk] carbazole compounds represented by the following formulas (1) and (2) to a glass transition temperature or higher. It can be manufactured by the step of dispersing.

In the step of dispersing the compounds represented by the above formulas (1) and (2) in the polymer, the polymer used is suitable to have high transparency and contain an aromatic ring. That is, polystyrene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate and the like can be exemplified, and those containing at least one of these are preferable.

Further, in this step, as a method of dispersing in the polymer, a method of dissolving in an organic solvent and mixing and then removing the solvent, and a method of heating and melting the polymer and mixing can be used, but the latter is more preferable. be.

As described above, this polymer composite material can be used as a phosphorescent material, a polarized light emitting material, and in the case of a phosphorescent material, it can be applied to an emergency sign, a dial, or the like. When this polymer composite material is used as a polarized light emitting material, it is possible to perform polarized light emission of deep blue color and high color purity by performing uniaxial stretching.

As described above, the present embodiment makes it possible to provide a novel and useful carbazole compound, a functional material containing the same, and a light emitting device.

Here, the compound according to the above embodiment was actually prepared and its effect was confirmed. Hereinafter, examples will be specifically described, but it goes without saying that the present invention is not limited to these specific examples.

The compounds obtained in the examples were subjected to melting point (mp), infrared spectroscopy (IR), nuclear magnetic resonance ( ¹ H NMR, ¹³ C NMR), matrix-assisted laser desorption / ionization (MALDI), and flight. It has been identified using a time-based (TOF) mass spectrometer (MS).

[Reference Example 1]
Synthesis of 9- (2-nitrophenyl) carbazole Potassium carbonate (33.06 g, 239.22 mmol) and 2-nitrofluorobenzene in a solution of carbazole (20.00 g, 119.61 mmol) in N, N-dimethylformamide (150 mL). Was added, and the mixture was stirred at 70 ° C. for 12 hours. The reaction mixture was poured into water (300 mL) and the precipitated precipitate was collected by filtration. The precipitate was washed with water (200 mL) and methanol (200 mL) to obtain 9- (2-nitrophenyl) carbazole represented by the following formula in a yield of 94% (32.41 g, 112.43 mmol) as yellow needle-like crystals. rice field. The data such as the melting point of this compound are as follows.

m. p. 154-155 ° C

IR (ATR, cm ^-1 ) ν 3051,160,1573,1523,1497,1477,1453,1443,1369,1350,1334,1316,1300,1228,1184,1150,1122,1108,1086,1019,1019 , 1002,994,957,942,917,872,849,782,748,725,704,667.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.09 (d, J = 8.0 Hz, 2H, 18-H), 7.28 (t, J = 7.2 Hz, 2H, 3,6-H), 7.36 (dd, J = 7.2,7.7 Hz, 2H, 2,7-H), 7.59-7.63 (m, 2H, 4,6-Hin2-ph), 7.77 (Dd, J = 7.6, 7.8 Hz, 1H, 5-H in ph), 8.09-8.14 (m, 3H, 4,5-H and 3-H in ph).

¹³ C NMR (100.5MHz, CDCl ₃ ) δ 109.03, 120.53, 120.63, 123.81, 125.88, 126.28, 129.10, 131.21, 131.35, 134. 19, 140.74, 147.35.

MALDI-TOF-MS (positive, dythranol) m / z calcd for C ₁₈ H ₁₂ N ₂ O ₂ : 288; found: 288 [M ⁺ ].

[Reference Example 2]
Synthesis of 9- (2-aminophenyl) carbazole 9- (2-nitrophenyl) carbazole (10.00 g, 34.69 mmol), iron powder (9.68 g, 173.43 mmol), and ammonium chloride (9) prepared above. .28 g, 173.43 mmol) was dispersed in an ethanol: water mixture (9: 1) and heated to reflux under a nitrogen atmosphere for 4 hours. The reaction mixture was hot filtered and the filtrate was allowed to stand at room temperature for 1 hour. The precipitated crystals were collected by filtration and washed with ethanol to obtain 9- (2-aminophenyl) carbazole represented by the following formula as colorless needle-like crystals in a yield of 86% (7.71 g, 29.83 mmol). The data such as the melting point of this compound were as follows.

m. p. 118-120 ° C

IR (ATR, cm ^-1 ) ν 3474, 3381, 3054, 1609, 1594, 1501, 1488, 1478, 1460, 1447, 1359, 1337, 1311, 1255, 1229, 1177, 1167, 1140, 1119, 1049, 1021 , 998, 940, 911, 850, 824, 774, 744, 724.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 3.00 (br-s, 2H, NH ₂ ), 6.91 (t, J = 7.7 Hz, 1H, 5-H in 9-aminophenyl), 6.96 (D, J = 8.0Hz, 1H, 3-H in 9-aminophenyl), 7.18 (d, J = 8.1Hz, 2H, 1,8-H in carbazole), 7.27-7.34 (M, 4H, ArH), 7.41 (t, J = 7.7Hz, 2H, 2,7-H in carbazole), 8.15 (d, J = 7.7Hz, 2H, 4,5-H) incarbazole).

¹³ C NMR (100.5MHz, CDCl ₃ ) δ 110.12, 116.52, 118.83, 119.86, 120.30, 122.27, 123.33, 126.00, 129.58, 129. 61, 160.62, 144.00.

MALDI-TOF-MS (positive, dithranol) m / z calcd for C18H14N2: 258; found: 258 [M ⁺ ].

[Reference Example 3]
Synthesis of Indro [3,2,1-jk] carbazole 9- (2-aminophenyl) carbazole (5.00 g, 19.36 mmol) was dissolved in acetic acid (50 mL) and concentrated sulfuric acid (5 mL) was added. The mixture was cooled to 15 ° C., an aqueous sodium nitrite solution (2.00 g, 29.04 mmol / 10 mL) was added dropwise over 10 minutes, and the mixture was stirred at 15 ° C. for 10 minutes. The mixture was heated under reflux at 130 ° C. for 30 minutes, allowed to cool to room temperature, and added to water (200 mL). The solid is collected by filtration, washed with water (100 mL) and methanol (100 mL), purified by column chromatography (BW300, toluene), recrystallized from dichloromethane / ethanol, and indro [3,2,1-jk] carbazole. Was obtained as a colorless powder in a yield of 60% (2.80 g, 11.62 mmol). The data such as the melting point of this compound were as follows.

m. p. 155-156 ° C

IR (ATR, cm ^-1 ) ν 3049, 1655, 1624, 1602, 1584, 1252, 1493, 1482, 1466, 1447, 1431, 1370, 1340, 1311, 1256, 1232, 1163, 1154, 1122, 1096, 1073 , 1039, 1012, 994, 964, 953, 928, 893, 854, 841, 815, 794, 748, 727, 684.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.36 (td, J = 7.6, 0.9 Hz, 2 H, 6, 10-H), 7.55 (td, J = 7.6, 0.9 Hz) , 2H, 5,11-H), 7.58 (t, J = 7.5Hz, 1H, 2-H), 7.91 (d, J = 7.6Hz, 2H, 7,9-H), 8.04 (d, J = 7.4Hz, 2H, 4,12-H), 8.14 (d, J = 7.7Hz, 2H, 1,3-H).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 122.22, 118.55, 119.45, 121.74, 122.89, 123.20, 126.74, 130.13, 138.79, 143. 84.

MALDI-TOF-MS (positive, dithranol) m / z calcd for C18H11N: 241; found: 241 [M ⁺ ].

[Reference example 4]
Synthesis of 2-bromoindro [3,2,1-jk] carbazole Indro [3,2,1-jk] carbazole (2.00 g, 8.29 mmol) was dissolved in chloroform (50 mL) and N-bromosuccinimide (1). A solution of .48 g, 8.29 mmol) in N, N-dimethylformamide (20 mL) was added dropwise over 10 minutes. The mixture was stirred at room temperature for 8 hours, washed with water (50 mL x 2), the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from dichloromethane / acetonitrile to obtain 2-bromoindro [3,2,1-jk] carbazole in a yield of 41% (1.09 g, 3.40 mmol) as a colorless powder. The data such as the melting point of this compound were as follows.

m. p. 204-206 ° C

IR (ATR, cm ^-1 ) ν 3053, 1652, 1603, 1569, 1496, 1468, 1445, 1415, 1368, 1339, 1301, 1268, 1229, 1163, 1151, 1135, 1084, 1049, 1030, 966, 927 , 879, 859, 844, 801, 776, 756, 736, 726, 660.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.36 (td, J = 7.7, 0.9 Hz, 2H, 6, 10-H), 7.57 (td, J = 7.7, 1.1 Hz) , 2H, 5,11-H), 7.88 (d, J = 8.1Hz, 2H, 7,9-H), 8.07 (d, J = 7.7Hz, 2H, 4,12-H) ), 8.15 (s, 2H, 1,3-H).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 122.22, 118.55, 119.45, 121.74, 122.89, 123.20, 126.74, 130.13, 138.79, 143. 84.

MALDI-TOF-MS (positive, dithranol) m / z calcd for C ₁₈ H ₁₀ BrN: 319; found: 319 [M ⁺ ].

[Reference Example 5]
2- (4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl) Indro [3,2,1-jk] Synthesis of carbazole 2-bromoindro [3,] under a nitrogen atmosphere 2,1-jk] Carbazole (1.00 g, 3.12 mmol), bis (pinacholate) diboron (0.95 g, 3.74 mmol), and potassium acetate (1.22 g, 12.48 mmol) degassed dimethyl sulfoxide. (15 mL) was added and heated to 100 ° C. [1,1'-Bis (diphenylphosphino) ferrocene] Dichloropalladium (II) dichloromethane adduct (127 mg, 0.16 mmol) was added, and the mixture was heated and stirred at 100 ° C. for 4 hours. The reaction mixture was added to water (100 mL) and extracted with chloroform (50 mL). The organic layer was washed with water (50 mL x 2), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue is purified by column chromatography (BW300, dichloromethane: hexane = 3: 2), recrystallized from dichloromethane / hexane, and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborola). N-2-yl) Indro [3,2,1-jk] carbazole was obtained as a colorless cubic crystal in a yield of 70% (802 mg, 2.18 mmol). The data such as the melting point of this compound were as follows.

IR (ATR, cm ^-1 ) ν 3054, 2976, 2924, 1648, 1603, 1585, 1504, 1469, 1449, 1420, 1402, 1368, 1377, 1329, 1308, 1297, 1264, 1246, 1220, 1209, 1164 , 1135, 1086, 1071, 1037, 962, 926, 885, 868, 846, 835, 781, 753, 741, 733, 702, 683, 659.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 1.44 (s, 12H, CH ₃ ), 7.36 (td, J = 7.7, 0.9 Hz, 2H, 6, 10-H), 7.55 (Td, J = 7.7, 1.1Hz, 2H, 5, 11-H), 7.91 (d, J = 8.1Hz, 2H, 7, 9-H), 8.13 (dt, J) = 7.7, 0.9 Hz, 2H, 4,12-H), 8.56 (s, 2H, 1,3-H).

¹³ C NMR (100.5MHz, CDCl ₃ ) δ 24.99, 83.81, 112.12, 118.22, 121.89, 123.15, 126.30, 126.64, 129.96, 138. 79, 145.86.

MALDI-TOF-MS (positive, dithranol) m / z calcd for C ₂₄ H ₂₂ BNO ₂ : 367; found: 367 [M ⁺ ].

[Reference Example 6]
(E) Synthesis of -3- (3-bromophenyl) -1-phenylprop-2-en-1-one 3-bromobenzaldehyde (10.00 g, 54.05 mmol) and acetophenone (6.49 g, 54.05 mmol) ) Was dissolved in ethanol (100 mL), sodium hydroxide (2.16 g, 54.05 mmol) was added, and the mixture was stirred for 4 hours. The precipitate was collected by filtration and washed with methanol (100 mL) to yield E) -3- (3-bromophenyl) -1-phenylprop-2-en-1-one in an 89% yield (13.81 g, 48. 10 mmol) was obtained as a colorless powder. The data such as the melting point of this compound were as follows.

m. p. 78-79 ° C

IR (ATR, cm ^-1 ) ν 3062,1656,1604,1593,1578,1553,1478,1448,1415,1345,1334,1305,1284,121,119,1181,1091,1073,1032,1014989 , 972,931,917,897,860,820,791,771,702,681,658.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.30 (t, J = 7.8 Hz, 1H, 5-H in 3-bromophenyl), 7.51 (d, J = 6.2 Hz, 1H, 6-H) in 3-bromophenyl), 7.52-7.56 (m, 3H, 2-Hand 3,5-H in 1-phenyl), 7.61 (tt, J = 7.3, 1.3Hz, 1H) , 4-H in 1-ph), 7.73 (d, J = 15.8Hz, 1H, 3-H), 7.80 (t, J = 1.7Hz, 1H, 2-H in 3-bromophenyl) ), 8.01 (d, J = Hz, 2H, 2,6-H in 1-phenyl).

¹³ C NMR (100.5MHz, CDCl ₃ ) δ 123.09, 123.26, 127.23, 128.54, 128.70, 130.46, 130.83, 133.01, 133.23, 137. 03, 137.90, 142.89, 189.98.

MALDI-TOF-MS (positive, dithranol) m / z calcd for C ₁₅ H ₁₁ BrO: 286; found: 287 [M + H] ⁺ .

[Reference Example 7]
Synthesis of 4- (3-bromophenyl) -2,6-diphenylpyrimidine (E) -3- (3-bromophenyl) -1-phenyl 4- (3-bromophenyl) -2,
Triethylamine (14.10 g, 139.32 mmol) and benzamidine hydrochloride (5.45 g, 34.) In an acetonitrile (100 mL) solution of 6-diphenylpyrimidineprop-2-en-1-one (10.00 g, 34.83 mmol). 83 mmol) was added, and the mixture was vigorously stirred at 50 ° C. for 24 hours. The reaction mixture was added to methanol (150 mL) and allowed to stand at room temperature for 6 hours. The precipitated precipitate was collected by filtration and washed with methanol (50 mL) to give 4- (3-bromophenyl) -2,6-diphenylpyrimidine as a colorless powder in a yield of 75% (10.12 g, 26.12 mmol). rice field. The data such as the melting point of this compound were as follows.

IR (ATR, cm ^-1 ) ν 3057, 1588, 1566, 1528, 1495, 1476, 1446, 1272, 1378, 1362, 1351, 1307, 1272, 1234, 1174, 1158, 1156, 1070, 1050, 1023, 997. , 924, 911, 863, 834, 807, 793, 774, 747, 698, 684, 660.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.44 (t, J = 7.6 Hz, 1H, 4-H in 4-bromophenyl), 7.53-7.59 (m, 6H, 3, 4, 5) -H in 2,6-phenyl), 7.67 (ddd, J = 8.2, 1.8, 0.9 Hz, 1H, 4-H in 4-bromophenyl), 7.98 (s, 1H, 5-H), 8.21 (ddd, J = 8.2,1.8, 0.9Hz, 1H, 6-H in 4-bromophenyl), 8.30 (m, 2H, 2,6-H in). 6-phenyl), 8.44 (t, J = 1.8 Hz, 1H, 2-H in 4-bromophenyl), 8.72 (m, 2H, 2,6-H in 2-phenyl).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 120.28, 123.21, 125.80, 127.30, 128.49, 128.94, 130.31, 130.39, 130.80, 130. 94, 133.61, 137.23, 137.87, 139.59, 163.16, 164.59, 164.99.

MALDI-TOF-MS (positive, dithranol) m / z calcd for C ₂₂ H ₁₅ BrN ₂ : 386; found: 387 [M + H] ⁺ .

[Example 1]
Synthesis of 2- [3- (2,6-diphenylpyrimidine-4-yl) phenyl] indro [3,2,1-jk] carbazole 4- (3-bromophenyl) -2,6-diphenylpyrimidine (844 mg, 2.18 mmol) and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) indro [3,2,1-jk] carbazole (800 mg, 2.18 mmol) Toluene (10 mL), ethanol (5 mL), and 2M sodium carbonate aqueous solution (10 mL) were added to the mixture, and the mixture was heated under a nitrogen atmosphere for 5 minutes and refluxed. Tetrakis (triphenylphosphine) palladium (0) (254 mg, 0.22 mmol) was added to the mixture, and the mixture was further heated to reflux for 8 hours. The reaction mixture was allowed to cool to room temperature, added to water (100 mL), and extracted with chloroform (50 mL x 2). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue is purified by column chromatography (BW300, chloroform), recrystallized from toluene, and 2- [3- (2,6-diphenylpyrimidine-4-yl) phenyl in a yield of 65% (778 mg, 1.42 mmol). ] Indro [3,2,1-jk] carbazole (ICzPyr) was obtained as a colorless powder. The data such as the melting point of this compound were as follows.

m. p. 254-255 ° C

IR (ATR, cm ^-1 ) ν 3055, 1656, 1589, 1568, 1530, 1497, 1452, 1430, 1398, 1380, 1356, 1298, 1260, 1245, 1230, 1175, 1157, 1133, 1087, 1073, 1047 , 1028, 1012, 1000, 970, 922, 903, 883, 863, 838, 805, 790, 777, 747, 727, 710, 691, 668.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.40 (t, J = Hz, 2H, 610-H), 7.51-7.61 (m, 8H), 7.71 (t, J = Hz, 1H, 3-H in 2-phenyl), 7.92-7.96 (m, 3H), 8.14 (s, 1H, 5-H in pyrimidine), 8.21 (d, J = Hz, 2H, 4,12-H), 8.30-8.35 (m, 5H), 8.63 (s, 1H), 8.76 (d, J = Hz, 2H)

MALDI-TOF-MS (positive, dithranol) m / z calcd for C ₄₀ H ₂₅ N ₃ : 547; found: 547 [M ⁺ ].

[Reference Example 8]
(E) Synthesis of -3- (4-bromophenyl) -1-phenylrop-2-en-1-one Acetophenone (3.25 g, 27.02 mmol) and 4-bromoabenzaldehyde (5.00 g, 27.02 mmol) An aqueous solution (5 mL) of an aqueous sodium hydroxide solution (216 mg, 5.40 mmol) was added to the methanol solution of the above. After stirring at room temperature for 6 hours, the precipitated precipitate was collected by filtration and washed with methanol to obtain the desired product as pale yellow needle-like crystals in a yield of 94% (7.29 g, 25.40 mmol). The data such as the melting point of this compound were as follows.

m. p. 97-98 ° C

IR (ATR, cm ^-1 ) 3057, 3028, 1656, 1600, 1583, 1575, 1560, 1496, 1484, 1449, 1396, 1364, 1334, 1289, 1276, 1126, 1179, 1159, 1106, 1065, 1035 1006, 995, 982, 955, 892, 874, 822, 791, 760, 727, 691, 665.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.39-7.42 (m, 3H, 3,4,5-H in 3-ph), 7.46 (d, J = 15.6 Hz, 1H, 2) -H), 7.61-7.64 (m, 4H, 3,5-H in 1-ph and 2,6-H in 3-ph), 7.80 (d, J = 15.6Hz, 1H) , 3-H), 7.87 (d, J = 7.9Hz, 2H, 2,6-H in 1-ph).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 121.43, 127.84, 128.47, 128.95, 129.97, 130.70, 131.88, 134.64, 136.88, 145. 33, 189.25.

MS (FAB) m / z 287 (79Br), 289 (81Br) ([M + 1] ⁺ ).

[Reference Example 9]
Synthesis of 4- (4-bromophenyl) -2,6-diphenylpyrimidine Compound (E) -3- (4-bromophenyl) -1-phenylrop-2-en-1-one (5.00 gm, 17) of Reference Example 1 above. Potassium carbonate (9.62 g, 69.64 mmol) and benzamidine hydrochloride (2.73 g, 17.41 mmol) were added to a solution of .41 mmol) in DMF (30 mL). The mixture was stirred at 70 ° C. for 24 hours, then poured into water (100 mL) and extracted with dichloromethane (50 mL). The organic layer was washed with water (50 mL x 2), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography, eluted with dichloromethane: hexane = 2: 1 (v / v), recrystallized from dichloromethane / ethanol, and the yield of the target product was 68% (4.58 g, 11.84 mmol). ) Was obtained as a colorless powder. The data such as the melting point of this compound were as follows.

m. p. 164-165 ° C

IR (ATR, cm ^-1 ) 3032, 1588, 1567, 1523, 1487, 1456, 1445, 1408, 1389, 1379, 1359, 1312, 1296, 1237, 1199, 1172, 1109, 1072, 1023, 1007, 932. 868, 823, 825, 807, 767, 749, 715, 686, 654.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.51-7.55 (m, 6H, 3,4,5-H in 2-ph and 3,4,5-H in 6-ph), 7.66 (D, J = 8.4Hz, 2H, 3,5-H in 4-ph), 7.93 (s, 1H, 5-H), 8.13 (d, J = 8.4Hz, 2H, 2) , 6-H in 4-ph), 8.25 (d, J = 7.5Hz, 2H, 2,6-H in 6-ph), 8.68 (d, J = 7.4Hz, 2H, 2) , 6-H in 2-ph).

¹³ C NMR (100.5MHz, CDCl ₃ ) δ 109.87, 125.37, 127.25, 128.43, 128.74, 128.89, 130.72, 130.86, 132.06, 136. 37, 137.30, 137.91, 163.51, 164.54, 164.93.

MS (EI) m / z 386 (79Br), 388 (81Br) ([M] ⁺ ).

[Comparative Example 1]
N, N-di ([1,1'-biphenyl] -4-yl) -4'-(2,6-diphenylpyrimidin-4-yl)-[1,1'-biphenyl] -4-amine synthesis reference Compounds 4- (4-bromophenyl) -2,6-diphenylpyrimidine (176 mg, 0.45 mmol) and [(4- (di ([1,1'-biphenyl] -4-yl) amino) boronic) of Example 2 Toluene (5 mL), ethanol (2 mL), and 2M aqueous sodium carbonate solution (5 mL) were added to acid] (200 mg, 0.45 mmol), respectively. The container was replaced with nitrogen, and the mixture was heated under reflux for 5 minutes in a nitrogen atmosphere, and then tetrakis (triphenylphosphine) palladium (0) (149 mg, 0.13 mmol) was added and the mixture was heated under reflux for another 4 hours. The reaction mixture was cooled to room temperature, washed with water (20 mL), and the organic layer was dried over anhydrous magnesium sulfate. This solution was poured into methanol, and the precipitated precipitate was collected by filtration and subjected to silica gel chromatography. Dichloromethane: hexane = 2: 1 (v / v) was used for elution and purification to obtain the desired product as a pale yellow powder with a yield of 63% (200 mg, 0.28 mmol). The data such as the melting point of this compound were as follows.

m. p. 246-247 ° C

IR (ATR, cm ^-1 ) 3030, 1598, 1588, 1567, 1516, 1482, 1447, 1395, 1362, 1320, 1292, 1278, 1263, 1177, 1111, 1074, 1026, 1005, 966, 922, 873 820, 757, 744, 721, 689, 655.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 725-7.28 (m, 6H, ArH), 7.32 (t, J = 7.3 Hz, 2H, 4'-H at biphenyl), 7.43 (T, J = 7.5Hz, 4H, 3', 5'-H in biphenyl), 7.52-7.53 (m, 16H, ArH), 7.79 (d, J = 8.4Hz, 2H) , 3,5-H in 4-ph at pyrimidine), 8.05 (s, 1H, 4-H in pyrimidine), 8.30 (dd, J = 1.7, 7.6 Hz, 2H, 2, 6) -H in 6-ph at pyrimidine), 8.37 (d, J = 8.4 Hz, 2H, 2,6-H in 4-ph at pyrimidine), 8.74 (dd, J = 1.7, 7) .8Hz, 2H, 2,6-H in 2-ph at pyrimidine).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 110.00, 124.11, 124.64, 126.70, 126.95, 127.28, 127.72, 127.91, 127.96, 128. 42, 128.49, 128.77, 128.88, 130.59, 130.71, 134.33, 135.88, 135.91, 137.61, 138.23, 140.53, 142.90, 146.68, 147.43, 164.27, 164.50, 164.68.

HRMS (FAB, PEG1000 as external standard) m / z calcd for C ₅₂ H ₃₇ N ₃ [M] ⁺ : 703.2987; found: 703.2986.

[Reference Example 10]
9- (4'-(2,6-diphenylpyrimidin-4-yl)-[1,1'-biphenyl] -4-yl) -9H-Carbazole Synthesis Compound 4- (4-bromophenyl)- 2,6-diphenylpyrimidine (1.00 g, 2.58 mmol) and [9- (4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) phenyl) -9H-carbazole] (917 mg, 2.58 mmol) was dissolved in toluene (10 mL), ethanol (5 mL) and 2M aqueous sodium carbonate solution (10 mL) were added, and the mixture was heated and refluxed in a nitrogen atmosphere for 5 minutes. Tetrakis (triphenylphosphine) palladium (0) (149 mg, 0.13 mmol) was added thereto, and the mixture was further heated under reflux for 4 hours, and then the reaction mixture was cooled to room temperature and washed with water (30 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography, eluted with dichloromethane: hexane = 2: 1 (v / v), recrystallized from dichloromethane / ethanol, and the desired product was obtained in a yield of 82% (1.16 g, 2.12 mmol). Obtained as a colorless powder. The data such as the melting point of this compound were as follows.

m. p. 187-188 ° C

IR (ATR, cm ^-1 ) 3039, 1588, 1568, 1522, 1496, 1478, 1450, 1244, 1395, 1381, 1361, 1335, 1319, 1301, 1226, 1171, 1118, 1074, 1027, 1004, 969, 932, 914, 871, 844, 823, 775, 741, 722, 689, 666.

¹ H NMR (400MHz, CDCl ₃ ) δ7.31 (t, J = 7.4Hz, 2H, 3,6-H in carbazole), 7.44 (t, J = 7.4Hz, 2H, 2,7) -H in carbasole), 7.49-7.58 (m, 8H, ArH), 7.68 (d, J = 8.4Hz, 2H, 3,5-H in 4-ph at pyrimline), 7. 87 (d, J = 8.2Hz, 2H, 3,5-H in biphenyl), 7.89 (d, J = 8.4Hz, 2H, 2', 6'-H in biphenyl), 8.07 (d, J = 8.2Hz, 2H, 3,5-H in biphenyl), 8.07 (d, J = 8.2Hz, 2H, 3,5-H in biphenyl) s, 1H, 5-H in pyrimidine), 8.16 (d, J = 7.4Hz, 2H, 4,5-H in carbazole), 8.32 (dd, J = 1.8, 7.5Hz, 2H, 2,6-H in 6-ph at pyrimidine), 8.42 (d, J = 8.2Hz, 2H, 2,6-H in biphenyl), 8.76 (dd, J = 1.8, 7.8Hz, 2H, 2,6-H in 2-ph at pyrimidine).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 109.79, 110.11, 120.05, 120.33, 123.47, 125.97, 127.27, 127.35, 127.47, 127. 84, 128.44, 128.48, 128.89, 130.65, 130.77, 136.66, 137.38, 137.49, 138.12, 139.22, 140.74, 142.45, 164.09, 164.52, 164.75.

HRMS (FAB) m / z calcd for C ₄₀ H ₂₇ N ₃ [M] ⁺ : 549.2205; found: 549.2206

[Reference Example 11]
Synthesis of 3,6-dibromo-9- (4'-(2,6-diphenylpyrimidin-4-yl)-[1,1'-biphenyl] -4-yl) -9H-carbazole Compound 9- (4'-(2,6-diphenylpyrimidin-4-yl)-[1,1'-biphenyl] -4-yl) -9H-carbazole (1.00 g, 1.82 mmol) in DMF (20 mL) solution with N -A solution of bromosuccinimide (648 mg, 3.64 mmol) in DMF (10 mL) was added dropwise at room temperature over 5 minutes. After stirring at room temperature for 2 hours, the reaction mixture was poured into methanol (50 mL) and allowed to stand for 8 hours. The precipitated precipitate was collected by filtration and washed with methanol (100 mL) to obtain the desired product as a colorless powder with a yield of 91% (1.17 g, 1.66 mmol). The data such as the melting point of this compound were as follows.

m. p. 253-255 ° C

IR (ATR, cm ^-1 ) 3038, 1676, 1604, 1588, 1566, 1520, 1495, 1467, 1435, 1397, 1361, 1136, 1277, 1226, 1172, 1120, 1057, 1021, 1004, 939, 854 822, 795, 775, 755, 740, 710, 685, 669.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.31 (d, J = 8.7 Hz, 1,8-H in carbasole), 7.51 (dd, J = 1.9, 8.8 Hz, 2H, 2) , 7-H in carbasole), 7.51-7.58 (m, 8H, ArH), 7.83 (d, J = 8.3Hz, 2H, 3,5-H in biphenyl), 7.87 ( d, J = 8.4Hz, 2H, 2', 6'-H in biphenyl), 8.05 (s, 1H, 5-H in pyrimidine), 8.18 (d, J = 1.9Hz, 2H, 4,5-H in carbasole), 8.30 (dd, J = 1.9, 7.5Hz, 2H, 3,5-H in 6-ph at pyrimidine), 8.41 (d, J = 8. 3Hz, 2H, 2,6-H in biphenyl), 8.75 (dd, J = 1.9, 7.8Hz, 2H, 2,6-H in 2-ph at pyrimidine).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 110.08, 111.50, 113.23, 123.27, 124.06, 127.21, 127.29, 127.50, 127.91, 128. 46, 128.50, 128.72, 128.92, 129.45, 130.69, 130.83, 136.39, 136.92, 137.47, 138.11, 139.73, 139.97, 142.13, 163.99, 164.55, 164.80.

HRMS (FAB) m / z calcd for C ₄₀ H ₂₅ Br ₂ N ₃ [M] ⁺ : 705.0415; found: 705.0415.

[Comparative Example 2]
9- (4'-(2,6-diphenylpyrimidin-4-yl)-[1,1'-biphenyl] -4-yl) -3,6-diphenyl-9H-carbazole Synthesis Compound 3, of Reference Example 4. 6-dibromo-9- (4'-(2,6-diphenylpyrimidin-4-yl)-[1,1'-biphenyl] -4-yl) -9Hcarbazole (1.00 g, 1.41 mmol) and phenylboronic acid ( 366 mg, 3.00 mmol) was dissolved in toluene (10 mL). Ethanol (5 mL) and a 2M aqueous sodium carbonate solution (10 mL) were added thereto, and the mixture was heated under reflux for 5 minutes under a nitrogen atmosphere. Tetrakis (triphenylphosphine) palladium (0) (162 mg, 0.14 mmol) was added, and the mixture was heated under reflux for another 6 hours, allowed to cool to room temperature, poured into water (100 mL), and extracted with chloroform (50 mL). After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, the residue was subjected to silica gel chromatography, eluted from chloroform: hexane = 2: 1 (v / v), purified, and the desired product yield 76. % (752 mg, 1.07 mmol) was obtained as a pale yellow powder. The data such as the melting point of this compound were as follows.

m. p. 310-311 ° C

IR (ATR, cm ^-1 ) 3035, 1600, 1588, 1568, 1521, 1495, 1474, 1458, 1243, 1363, 1312, 1296, 1280, 1267, 1232, 1172, 1135, 1121, 1074, 1027, 1004 970, 944, 930, 916, 879, 852, 843, 817, 805, 763, 745, 734,688.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.36 (t, J = 7.5 Hz, 2H, 4-H in 3,6-ph at carbasole), 7.49 (t, J = 7.5 Hz, 4H, 3,5-H in 3,6-ph at carbazole), 7.53-7.58 (m, 8H, ArH), 7.69-7.75 (m, 8H, ArH), 7.90 (D, J = 8.2Hz, 2H, 3,5-H in biphenyl), 7.94 (d, J = 8.2Hz, 2H, 2', 6'-H in biphenyl), 8.09 (s) , 1H, 4-H impylmidine), 8.33 (d, J = 7.8Hz, 2H, 2,6-H in 6-ph at pyrimidine), 8.42 (s, H, 4,5-H in) carbazole), 8.45 (d, J = 8.2Hz, 2H, 2,6-H in biphenyl), 8.77 (d, J = 7.82, 6-H in 2-ph at pyrimidine).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 110.13, 110.21, 118.90, 124.18, 125.73, 126.63, 127.21, 127.30, 127.51, 127. 89, 128.45, 128.50, 128.60, 128.79, 128.91, 130.67, 130.80, 133.81, 136.77, 137.31, 137.53, 138.15, 139.38, 140.66, 141.83, 142.41, 164.12, 164.57, 164.81.

HRMS (FAB) m / z calcd for C ₅₂ H ₃₅ N3 [M] ⁺ : 701.2831; found: 701.2829.

[Reference Example 12]
Synthesis of 3,6-dibromo-9- (2-nitrophenyl) -9H-carbazole. A solution of NBS (33.96 g, 190.78 mmol) in DMF (150 mL) to a solution of compound 9- (2-nitrophenyl) -9H-carbazole (25.00 g, 86.72 mmol) of Reference Example 5 at room temperature. It was dropped over 20 minutes. After stirring the mixture at room temperature for 4 hours, the reaction mixture was poured into 500 mL of water). The precipitated precipitate was collected by filtration and washed with methanol (200 mL) to obtain the desired product as yellow needle-like crystals in a yield of 76% (29.40 g, 65.91 mmol). The data such as the melting point of this compound were as follows.

m. p. 202-203 ° C

IR (ATR, cm ^-1 ) 3083, 1599, 1523, 1495, 1466, 1429, 1362, 1318, 1297, 1285, 1230, 1179, 1157, 1142, 1123, 1089, 1057, 1020, 992, 961, 942 932, 891, 876, 849, 817, 795, 777, 748, 727, 712, 676, 665.

¹ H NMR (400 MHz, CDCl ₃ ) δ 6.96 (d, J = 8.6 Hz, 2H, 1,8-H in carbasole), 7.49 (dd, J = 1.9, 8.6 Hz, 2H) , 2,7-H in carbasole), 7.62 (d, J = 7.7Hz, 1H, 6-H in ph), 7.73 (t, J = 7.7Hz, 1H, 4-H in ph) ), 7.86 (t, J = 7.7 Hz, 1H, 5-H in ph), 8.17-8.19 (m, 3H, 4,5-H in carbazole and 3-H in ph).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 110.76, 113.87, 123.54, 124.38, 126.13, 129.80, 129.89, 130.21, 131.26, 134. 50, 139.82, 147.17.

HRMS (EI) m / z calcd for C ₁₈ H ₁₀ Br ₂ N ₂ O ₂ [M] ⁺ : 443.9109; found: 443.9108.

[Reference Example 13]
Synthesis of 9- (2-nitrophenyl) -3,6-diphenyl-9H-carbazole Compound 3,6-dibromo-9- (2-nitrophenyl) -9H-carbazole (25.00 g, 56.04 mmol) of Reference Example 6 And phenylboronic acid (15.03 g, 123.29 mmol) were dispersed in a mixed solvent of toluene: ethanol = 5: 1 (v / v), and a 2M aqueous sodium carbonate solution (100 mL) was added. The container was replaced with nitrogen and heated to reflux for 5 minutes, then tetrakis (triphenylphosphine) palladium (0) (324 mg, 0.28 mmol) was added, and the mixture was heated to reflux for another 2 hours. The reaction mixture was poured into water (200 mL) and extracted with toluene (50 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained solid was subjected to silica gel chromatography, eluted with toluene, purified, and then recrystallized from acetone / methanol to obtain the desired product as an orange powder in a yield of 93% (22.96 g, 52.12 mmol). .. The data such as the melting point of this compound were as follows.

m. p. 150-151 ° C

IR (ATR, cm ^-1 ) 3026, 1598, 1571, 1533, 1492, 1475, 1457, 1437, 1369, 1357, 1337, 1297, 1283, 1269, 1223, 1185, 1162, 1143, 1130, 1088, 1076. 1040, 1019, 1010, 996, 967, 937, 915, 886, 859, 846, 810, 778, 755, 138, 729, 695.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.17 (d, J = 8.5 Hz, 2H, 1,8-H in carbasole), 7.34 (t, J = 7.4 Hz, 2H, 4-H) in 3,6-ph), 7.47 (t, J = 7.7Hz, 4H, 3,5-H in 3,6-ph), 7.63 (dd, J = 1.8, 8.4Hz) , 2H, 2,7-H incarbazole), 7.66-7.71 (m, 6H, ArH), 7.84 (dt, J = 1.5, 7.7Hz, 1H, 6-H in 9- ph), 8.19 (dd, J = 1.6, 8.1Hz, 1H, 3-H in 9-ph), 8.37 (d, J = 1.7Hz, 2H, 4,5-H in) carbazole).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 109.56, 119.34, 124.61, 126.21, 126.86, 127.49, 128.92, 129.39, 131.41, 134. 50, 134.55, 140.76, 141.81.

HRMS (EI) m / z calcd for C ₃₀ H ₂₀ N ₂ O ₂ [M] ⁺ : 440.1525; found: 440.1526.

[Reference Example 14]
Synthesis of 9- (2-aminophenyl) -3,6-diphenyl-9H-carbazole Compound 9- (2-nitrophenyl) -3,6-diphenyl-9H-carbazole (20.00 g, 45.40 mmol) of Reference Example 7. ) Was dispersed in ethanol (150 mL) and 5% palladium carbon (500 mg) was added. Hydrazine monohydrate (12.52 g, 0.25 mol) was added thereto, and the mixture was heated under reflux in a nitrogen atmosphere for 28 hours. The reaction mixture was hot filtered to remove palladium carbon and the filtrate was allowed to cool at room temperature for 2 hours. The precipitated precipitate was collected by filtration and washed with methanol (100 mL) to obtain the desired product as colorless plate-like crystals in a yield of 80% (14.91 g, 36.32 mmol). The data such as the melting point of this compound were as follows.

m. p. 123-124 ° C

IR (ATR, cm ^-1 ) 3475, 3380, 3061, 1728, 1628, 1614, 1597, 1508, 1498, 1474, 1458, 1436, 1365, 1310, 1296, 1267, 1239, 1189, 1172, 1159, 1137, 1095, 1077, 1042, 1028, 1009, 984, 945, 912, 880, 844, 825, 759, 744, 736, 696, 671.

¹ H NMR (400 MHz, CDCl ₃ ) δ 3.61 (s, 2H, NH ₂ ), 6.94 (t, J = 7.5 Hz, 1H, 5-H in 9-ph), 6.98 (d) , J = 8.5Hz, 1H, 3-H in 9-ph), 7.24-7.36 (m, 6H, 1,8-H in carbazole, 4-and 6-H in 9-ph, and 4-H in 3,6-ph), 7.47 (t, J = 7.7Hz, 4H, 3,5-H in 3,6-ph), 7.66 (dd, J = 1.7, 8.5Hz, 2H, 2,7-H in carbazole), 7.72 (d, J = 7.7Hz, 4H, 2,6-H in 3,6-ph), 8.40 (s, 2H, 4,5-H in carbazole).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 110.52, 116.64, 118.94, 122.16, 123.98, 125.78, 126.59, 127.34, 128.78, 129. 52, 129.74, 133.63, 140.56, 141.93, 143.95.

HRMS (EI) m / z calcd for C ₃₀ H ₂₂ N ₂ [M ⁺ ]: 410.1783; found: 410.1782.

[Reference Example 15]
Synthesis of 2,11-diphenyllindolo [3,2,1-jk] carbazole Compound 9- (2-aminophenyl) -3,6-diphenyl-9H-carbazole (10.00 g, 24.36 mmol) of Reference Example 8 is acetic acid. It was dissolved in (100 mL). Concentrated sulfuric acid (10 mL) was slowly added to this solution and then cooled to 10 ° C. An aqueous solution (10 mL) of sodium nitrite (1.73 g, 25.07 mmol) was added dropwise thereto at the same temperature over 15 minutes, and the mixture was further stirred for 5 minutes. The obtained dark red solution was immediately heated to the reflux temperature and refluxed by heating for 2 hours. The reaction mixture was allowed to cool to room temperature and then poured into water (200 mL). The precipitate was collected by filtration, washed with methanol (100 mL), and then subjected to silica gel chromatography. After eluting with chloroform and purifying, the substance was recrystallized from dichloromethane / ethanol to obtain the desired product as a pale yellow powder in a yield of 60% (5.75 g, 14.62 mmol). The data such as the melting point of this compound were as follows.

m. p. 193-194 ° C

IR (ATR, cm ^-1 ) 3028, 1656, 1593, 1565, 1513, 1489, 1459, 1489, 1429, 1367, 1339, 1321, 1296, 1257, 1234, 1120, 1185, 1165, 1156, 1134, 1104 1090, 1077, 1035, 1014, 967, 928, 885, 866, 815, 776, 760, 741, 731, 698, 675, 660.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.30 (t, J = 7.5 Hz, 1H, 11-H), 7.34-7.39 (m, 2H, 4-H in 2,5- ph), 7.45-7.51 (m, 5H, ArH), 7.67-7.77 (m, 7H, ArH), 8.06 (d, J = 7.7Hz, 1H, 12-H) ), 8.13 (s, 1H, 1-or 3-H), 8.16 (s, 1H, 1-or 3-H), 8.25 (d, J = 1.8Hz, 1H, 4- H).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 112.35, 118.68, 119.30, 119.43, 121.85, 121.89, 123.28, 126.12, 126.71, 126. 95, 127.05, 127.38, 128.37, 128.91, 128.98, 130.15, 130.68, 135.19, 137.69, 138.37, 139.04, 141.52 143.47, 143.99.

HRMS (EI) m / z calcd for C ₃₀ H ₁₉ N [M ⁺ ]: 393.1517; found: 393.1518.

[Reference Example 16]
Synthesis of 5-bromo-2,11-diphenyllindolo [3,2,1-jk] carbazole Compound 2,11-diphenyllindolo [3,2,1-jk] carbazole (5.00 g, 12.71 mmol) of Reference Example 9 Was dissolved in chloroform (50 mL). A solution of N-bromosuccinimide (2.26 g, 12.71 mmol) in DMF (20 mL) was added dropwise to this solution at room temperature over 10 minutes. After stirring the mixture for 8 hours, chloroform was distilled off under reduced pressure, and methanol was added to the residue. The precipitated precipitate was collected by filtration and washed with methanol (100 mL) to obtain the target product 12 [5-bromo-2,11-diphenyllindolo [3,2,1-jk] carbazole] in a yield of 97% (5.82 g, 12.33 mmol) was obtained as a colorless powder. The data such as the melting point of this compound were as follows.

m. p. 233-235 ° C

IR (ATR, cm ^-1 ) 3058, 3031, 1659, 1594, 1557, 1482, 1461, 1440, 1420, 1371, 1332, 1318, 1293, 1263, 1229, 1200, 1164, 1139, 1105, 1077, 1051, 1039, 1016, 1007, 961, 946, 932, 911, 885, 867, 832, 815, 790, 754, 743, 688, 664.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 7.36-7.41 (m, 2H, 4-Hin ph), 7.47-7.53 (m, 6H, ArH), 7.65-7. 70 (m, 6H, ArH), 8.04 (d, J = 0.9Hz, 1H, 1-or 3-H), 8.11 (s, 1H, 12-H), 8.13 (d, J = 0.9Hz, 1H, 1-or 3-H), 8.22 (s, 1H, 4-H).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 112.13, 113.07, 114.60, 117.31, 118.65, 119.33, 119.77, 121.75, 125.95, 126. 11, 126.71, 127.01, 127.21, 128.14, 128.82, 128.85, 129.28, 130.41, 131.46, 135.37, 137.26, 137.82, 137.91, 141.15, 142.94, 143.91.

HRMS (EI) m / z calcd for C ₃₀ H ₁₈ BrN [M ⁺ ]: 471.0623; found: 471.0623.

[Reference Example 17]
2,11-diphenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxabolone-2-yl) indole [3,2,1-jk] Synthesis of carbazole Compound 5 of Reference Example 10. -Bromo-2,11-diphenyllindolo [3,2,1-jk] carbazole (5.00 g, 10.58 mmol), bis (pinacolato) divoron (2.79 g, 11.00 mmol), and potassium acetate (4.00 g). DMSO (50 mL) degassed under a nitrogen atmosphere was added to (40.75 mmol), and the temperature of the mixture was raised to 100 ° C. To this, [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane adduct (433 mg, 0.53 mmol) was added, and the mixture was stirred at the same temperature for 4 hours. The reaction mixture was poured into water (100 mL) and extracted with chloroform (50 mL). The organic layer was washed with water (50 mL x 2), dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel chromatography, eluted with chloroform, purified, and then recrystallized from dichloromethane / hexane to obtain the desired product as a colorless powder in a yield of 75% (4.12 g, 7.94 mmol). The data such as the melting point of this compound were as follows.

m. p. 162-164 ° C

IR (ATR, cm ^-1 ) 3054, 3032, 2976, 2926, 1658, 1599, 1571, 1484, 1455, 1438, 1245, 1378, 1350, 1331, 1315, 1304, 1294, 1262, 1216, 1202, 1167, 1147, 1107, 1067, 1016, 966, 951, 917, 913, 882, 862, 847, 799, 758, 750, 699, 680, 664.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ 1.44 (s, 12H, CH ₃ ), 7.36-7.41 (m, 2H, 4-H in ph), 7.47-7.59 (m) , 4H, 3,5-H in ph), 7.71-7.77 (m, 5H, 2,6-H in ph and 6-H), 7.87-7.93 (m, 2H, 7) -And 9-H), 8.03 (d, J = 8.0Hz, 1H, 10-H), 8.23 (s, 1H, 3-H), 8.23 (s, 1H, 4-H) ), 8.33 (s, 1H, 1-H), 8.64 (s, 1H, 12-H).

¹³ C NMR (100.5 MHz, CDCl ₃ ) δ 24.98, 26.91, 83.90, 111.66, 112.58, 118.66, 118.75, 119.22, 119.51, 121. 82, 126.11, 126.60, 126.97, 127.27, 128.19, 128.80, 128.84, 129.65, 130.11, 130.84, 133.59, 135.49, 137.94, 138.22, 140.90, 141.34, 143.28, 144.10.

HRMS (EI) m / z calcd for C ₃₆ H ₃₀ BNO ₂ : 519.2370; found: 519.2370.

[Example 2]
5- (4- (2,6-diphenylpyrimidin-4-yl) phenyl) -2,11-diphenyllindolo [3,2,1-jk] Synthesis of carbazole Compound 2,11-diphenyl-5 (2,11-diphenyl-5) of Reference Example 11 4,4,5,5-tetramethyl-1,3,2-dioxabolone-2-yl) indole [3,2,1-jk] carbazole (1.34 g, 2.58 mmol) and 2 (1.00 g, 2.58 mmol) was dissolved in toluene (20 mL). Ethanol (10 mL) and a 2M aqueous sodium carbonate solution (10 mL) were added to this solution, the container was replaced with nitrogen, and the mixture was heated under reflux for 5 minutes under a nitrogen atmosphere. Tetrakis (triphenylphosphine) palladium (0) (149 mg, 0.13 mmol) was added thereto, and the mixture was heated under reflux for another 8 hours. Since the product was extremely sparingly soluble, purification was carried out by the method described below. First, the aqueous layer was removed with a pipette, the organic layer was filtered and the precipitate was filtered off. The obtained solid was washed with water (50 mL), methanol (50 mL), acetone (50 mL) and chloroform (50 mL) in this order, and then sublimated and purified at 5x10-4Pa at 410 ° C. to obtain a yield of 70%. (1.26 g, 1.81 mmol) was obtained as pale yellow needle-like crystals.

m. p. 360-361 ° C

IR (ATR, cm ^-1 ) 3035, 1656, 1599, 1587, 1565, 1255, 1515, 1496, 1843, 1464, 1443, 1426, 1399, 1363, 1332, 1292, 1259, 1236, 1202, 1167, 1142 1104, 1075, 1036, 1024, 948, 930, 888, 866, 841, 814, 805, 777, 753, 735, 686, 667, 655.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.38-7.40 (m, 2H, 4-H in 2,6-ph at ICz), 7.50-7.61 (m, 10H, ArH), 7.77 (d, J = 7.2Hz, 2H, 2,6-H in 2- or 5-ph at ICz), 7.81 (d, J = 7.8Hz, 2H, 2,6-H in) 2- or 5-ph at ICz), 7.85 (dd, J = 1.8, 8.4Hz, 1H, 6-H in ICz), 7.94 (dd, J = 1.8, 8.2Hz) , 1H, 10-H in ICz), 8.03 (d, J = 8.6Hz, 1H, 7-H in ICz), 8.06 (d, J = 8.3Hz, 8-H in ICz), 8.11 (s, 1H, 5-H in pyrimidine), 8.33-8.36 (m, 4H, ArH), 8.42 (d, J = 1.8Hz, 1H, 4-H in ICz) , 8.46 (d, J = 8.2Hz, 2H, 2,6-H in 4-ph at pyrimidine), 8.51 (d, J = 1.8Hz, 1H, 12-H in ICz), 8 .77 (dd, J = 1.5, 7.9 Hz, 2H, 2,6-H in 2-ph at pyrimidine).

* ¹³ C NMR coildn't be measured due to pore solubility of this compact

MS (FAB) m / z 699 [M] ⁺ , 700 ([M + 1] ⁺ .

Anal. Calcd for C ₅₂ H ₃₃ N ₃ : C, 89.24; H, 4.75; N, 6.00. Found: C, 89.47; H, 4.55; N, 5.79.

Table 1 shows the basic physical characteristics of the compound of Example 1. The optical band gap (ΔE (S1 − S ₀ )) obtained from the absorption edge wavelength of the UV / Vis absorption spectrum is as large as 3.04 eV, and the triplet excitation energy (ΔE (T ₁ − S ₀ )) is also 2.83 _eV . This is a sufficient value as a host material for green phosphorescent materials and TADF materials. The first oxidation potential (E _ox ) determined by DPV measurement is 0.96 eV, the first reduction potential (E _red is -2.33 eV), and it has an appropriate affinity for both holes and electrons, that is, bipolarity. It was found. The ionization potential (Ip) determined by photoelectron spectroscopy was 5.90 eV, which is appropriate as a host material. The melting point (T _m ) was 255 ° C, and the glass transition temperature (T _g ) was 110 ° C, which are common. It showed a sufficiently large value as compared with the host material CBP (84 ° C.) and the like. The thermal decomposition temperature (T _d ) was also 398 ° C., showing sufficient heat resistance that can be used in the vacuum vapor deposition process.

[Example 3]
A TADF organic EL device using the compound of Example 1 as a host material was produced by vacuum deposition. The device structure is ITO (110) / HAT-CN (10) / Tris-PCz (30) / mCBP or [Example 1] + 10% 4CzIPN (30) / T2T (10) / BPy-TP2 (40) / LiF. (0.8) / Al (100). The device characteristics are shown in FIG.

[Comparative Example 3]
A TADF organic EL device using mCBP as a host material was produced. Except for the host material, both the device structure and the manufacturing method were exactly the same as in Example 3. The device characteristics are shown in FIG.

The drive voltage of the device of Example 3 was significantly lower than that of Comparative Example 3 (FIG. 1a), and the current efficiency and power efficiency were also significantly higher (FIGS. 1b and 1c). Furthermore, it was confirmed that the LT ₅₀ reached 5 times (Fig. 1d) and had a great advantage in terms of durability. From the above results, it was found that the compound of Example 1 has higher performance than the existing material in terms of both efficiency and durability as a host material for the TADF organic EL device.

Further, FIG. 2 shows the fluorescence spectra of the compound of Example 2, the compound of Comparative Example 1 and Comparative Example 2 having a similar structure, and the toluene solution of the general light emitting material TBPe. Since the compound of Example 2 has a shorter emission wavelength and a significantly narrower full width at half maximum of the spectrum than any of the other compounds, it was confirmed that the compound has a deep blue emission characteristic with high color purity.

[Example 4]
0.5% by weight of the compound of Example 2 was added to 1 g of polyethylene terephthalate heated and melted at 285 ° C., and the mixture was stirred until uniform. This was rapidly cooled with water to produce a transparent composite. FIG. 3 shows a state after irradiating this with UV light (365 nm) and stopping the irradiation.

[Comparative Example 4]
Further, 0.5% by weight of the compound of Comparative Example 1 was added to 1 g of polyethylene terephthalate heated and melted at 285 ° C., and the mixture was stirred until uniform. This was rapidly cooled with water to produce a transparent composite. FIG. 3 shows a state after irradiating this with UV light (365 nm) and stopping the irradiation.

[Comparative Example 5]
Further, 0.5% by weight of the compound of Comparative Example 2 was added to 1 g of polyethylene terephthalate heated and melted at 285 ° C., and the mixture was stirred until uniform. This was rapidly cooled with water to produce a transparent composite. FIG. 3 shows a state after irradiating this with UV light (365 nm) and stopping the irradiation.

Further, when the composite material of Example 4 was irradiated with UV light (365 nm), green afterglow was visually observed for 10 seconds or more even after the irradiation was stopped. Afterglow was also observed in the composites of Comparative Example 4 and Comparative Example 5, but the emission time was significantly shorter than that of Example 4, confirming that the composite of Example 4 is promising as an organic phosphorescent material. rice field.

[Example 5]
The polymer composite of Example 4 was uniaxially stretched while being heated with a heat gun to prepare a film.

[Comparative Example 6]
The polymer composite of Comparative Example 4 was uniaxially stretched while being heated with a heat gun to prepare a film.

[Comparative Example 7]
The polymer composite of Comparative Example 5 was uniaxially stretched while being heated with a heat gun to prepare a film.

FIG. 4 shows photographs of the films of Example 5, Comparative Example 6, and Comparative Example 7 irradiated with UV light (365 nm) and observed through a polarizing plate. In the figure, the stretching direction is the long axis direction of the film, and the white arrow indicates the polarization axis of the polarizing plate.

It was confirmed that the light emission of the film of Comparative Example 6 was hardly polarized and was polarized to some extent in Comparative Example 6, but the light emission of the film of Example 5 was significantly polarized as compared with these. ..

The spectrum measured by Konica Minolta CS-2000 is shown in FIG. In the figure, "//" means that the polarization axis of the polarizing plate is parallel to the stretching direction, and "⊥" indicates that the polarization axis of the polarizing plate is perpendicular to the stretching direction. It can be seen that the light emission of the film of Example 5 is significantly polarized as compared with Examples 7 and 8, and the light emission is realized in deep blue with a narrow spectrum half width. Therefore, the film of Example 9 is promising as a polarized light emitting material having a deep blue color and high color purity.

Claims (11)

1. An indro [3,2,1-jk] carbazole compound represented by the following formula (1).
   

   

   (In the above general formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, polycyclic aromatic hydrocarbon groups, or , X ₁ , X ₂ , and X ₃ each independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ in the above formula. One is a nitrogen atom.)
2. An indro [3,2,1-jk] carbazole compound represented by the following formula (2).
   

   

   (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, polycyclic aromatic hydrocarbon groups, or Represents a heteroaromatic ring group. In the above formula, X ₁ , X ₂ , and X ₃ independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ is represented. One is a nitrogen atom.)
3. A functional material containing at least one of the compound according to claim 1 and the compound according to claim 2.
4. The functional material according to claim 3, which is a light emitting material.
5. The functional material according to claim 3, which is a host material.
6. A light emitting device containing the functional material according to claim 3.
7. A polymer composite material containing at least one of the compound according to claim 1 and the compound according to claim 2.
8. A functional material containing the polymer composite material according to claim 7.
9. The functional material according to claim 8, which is a phosphorescent material.
10. The functional material according to claim 8, which is a polarized light emitting material.
11. Glass of at least one of the indro [3,2,1-jk] carbazole compound represented by the following formula (1) and the indro [3,2,1-jk] carbazole compound represented by the following formula (2). A method for producing a polymer composite material, which comprises a step of dispersing in a polymer heated above a transition temperature.
    

    

    

    (In the above formula, R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, phenyl groups, cyano groups, polycyclic aromatic hydrocarbon groups, or Represents a heteroaromatic ring group. In the above formula, X ₁ , X ₂ , and X ₃ independently represent a nitrogen atom or a hydrogen-substituted carbon atom, but at least one of X ₁ , X ₂ , and X ₃ is represented. One is a nitrogen atom.)

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