Fluorene compound and organic luminescent device using the same

This is a national stage of PCT/JP03/10259 filed Aug. 12, 2003.

The present invention relates to a novel organic compound and an organic luminescent device using the same.

An organic luminescent device is a device where a thin film containing a fluorescent organic compound or a phosphorescent organic compound is sandwiched between an anode and a cathode; an electron and a hole injected from the respective electrodes generate an exciton of the fluorescent compound or the phosphorescent compound; and light emitted when the exciton returns to a ground state is utilized.

According to a study of Kodak company in 1987 (Appl. Phys. Lett. 51, 913 (1987)), there has been reported a luminescence of approximately 1000 cd/m 2 at an applied voltage of approximately 10 V in a device having a separated-function type two-layer structure using ITO as an anode, a magnesium-silver alloy as a cathode, an aluminum quinolinol complex as an electron transport material and a luminescent material, and a triphenyl amine derivative as a hole transport material. The related patents include U.S. Pat. Nos. 4,539,507, 4,720,432, 4,885,211, and so on.

In addition, it is possible to generate a luminescence from ultraviolet to infrared ones by changing the kinds of the fluorescent organic compound, and in recent years, extensive studies have been made on various kinds of compounds. For instance, such compounds are disclosed in U.S. Pat. Nos. 5,151,629, 5,409,783 and 5,382,477, Japanese Patent Application Laid-Open Nos. 2-247278, 3-255190, 5-202356, 9-202878, 9-227576, and so on.

In recent years, many studies have been made on an application of energy in a triplet state to an EL using phosphorescent compounds as luminescent materials. A high luminous efficiency exhibited by an organic luminescent device using an iridium complex as a luminescent material has been reported by a group at Princeton University (Nature 395, 151 (1998)).

Furthermore, in addition to the organic luminescent device using a low molecular weight material as mentioned above, an organic luminescent device using a conjugated polymer has been reported by a group at Cambridge University (Nature, 347, 539 (1990)). In this report, a luminescence from a single layer is confirmed through film formation of polyphenylene vinylene (PPV) using a coating system.

The related patents of the organic luminescent device using the conjugated polymer include U.S. Pat. Nos. 5,247,190, 5,514,878, 5,672,678, Japanese Patent Application Laid-Open Nos. 4-145192 and 5-247460, and so on.

In this way, a recent progress in the organic luminescent device is remarkable, and characteristics thereof suggest a possibility of applications for various purposes, which enable the luminescent device with a high luminance even at a low applied voltage, a wide variety of luminous wavelengths, a high-speed response, and a thin and lightweight form.

However, an optical output with a higher luminance or higher conversion efficiency is required under the present conditions. In addition, many problems still remain to be solved regarding a durability against a change with time due to a long-term use, deterioration caused by an atmospheric gas containing oxygen, moisture, or the like. Furthermore, it is not still insufficient for solving problems related to the needs for luminescences of blue, green, and red having high color purity when considering the applications to a full color display and the like.

An object of the present invention is to provide a novel fluorene compound.

Also, another object of the present invention is to provide an organic luminescent device using a specific fluorene compound, which has an optical output with an extremely high efficiency and a high luminance.

In addition, another object of the present invention is to provide an organic luminescent device having an extremely high durability.

Furthermore, another object of the present invention is to provide an organic luminescent device that can be easily produced at relatively low costs.

Accordingly, a fluorene compound according to the present invention is represented by the following general formula [I]:

(wherein R 1 and R 2 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a cyano group, or a halogen atom, in which R 1 themselves or R 2 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 1 and R 2 which are bonded to the same fluorene group may be identical to or different from each other; R 3 and R 4 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, in which R 3 themselves or R 4 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 3 and R 4 which are bonded to the same fluorene group may be identical to or different from each other; Ar 1 and Ar 2 represent a substituted or unsubstituted fused polycyclic aromatic group having at least three benzene rings in total or a substituted or unsubstituted fused polycyclic heterocyclic group bonded to the fluorene group with a carbon atom and having at least three rings including a benzene ring and a heterocyclic ring in total, in which Ar 1 and Ar 2 may be identical to or different from each other; and n represents an integer of 1 to 10, preferably 1 to 3.)

Further, as a preferable form, an organic luminescent device according to the present invention includes at least a pair of electrodes including an anode and a cathode and one or a plurality of layers containing an organic compound sandwiched between the pair of electrodes, in which at least one of the layers containing the organic compound contains at least one of the fluorene compounds.

FIG. 1 is a cross-sectional view showing an example of the organic luminescent device in accordance with the present invention.

FIG. 2 is a cross-sectional view showing another example of the organic luminescent device in accordance with the present invention.

FIG. 3 is a cross-sectional view showing still another example of the organic luminescent device in accordance with the present invention.

FIG. 4 is a cross-sectional view showing still another example of the organic luminescent device in accordance with the present invention.

FIG. 5 is a cross-sectional view showing still another example of the organic luminescent device in accordance with the present invention.

FIG. 6 is a cross-sectional view showing still another example of the organic luminescent device in accordance with the present invention.

Hereinafter, the present invention will be described in detail.

First, the fluorene compound of the present invention will be described.

The fluorene compound of the present invention is represented by the above general formula [I].

Here, at least one of Ar 1 and Ar 2 is preferably a fused polycyclic aromatic group represented by the following general formula [II]:

(wherein R 5 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a cyano group, or a halogen atom.)

Furthermore, the fluorene compound of the present invention is more preferably represented by one of the following structural formulas:

Further, at least one of Ar 1 and Ar 2 is preferably a fused polycyclic aromatic group represented by one of the following general formulae [III] to [IX]:

(wherein R 6 to R 12 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted amino group, a cyano group, or a halogen atom.)

Specific examples of substituents in the above general formula [I] to the above general formula [IX] will be shown below.

As the alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an octyl group, and the like can be given.

As the aralkyl group, a benzyl group, a phenethyl group, and the like can be given.

As the aryl group, a phenyl group, a biphenyl group, a terphenyl group, and the like can be given.

As the heterocyclic group, a thienyl group, a pyrrolyl group, a pyridyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a thiadiazolyl group, a terthienyl group, and the like can be given.

As the substituted amino group, a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, a ditolylamino group, a dianisolylamino group, and the like can be given.

As the halogen atom, fluorine, chlorine, bromine, iodine, and the like can be given.

As the fused polycyclic aromatic group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a triphenylenyl group, a perylenyl group, and the like can be given.

As the fused polycyclic heterocyclic group, a carbazolyl group, an acridinyl group, a phenanthrolyl group, and the like can be given.

As substituents which the above-mentioned substituents may have, alkyl groups such as a methyl group, an ethyl group, and a propyl group; aralkyl groups such as a benzyl group and a phenethyl group; aryl groups such as a phenyl group and a biphenyl group; heterocyclic groups such as a thienyl group, a pyrrolyl group, and a pyridyl group; amino groups such as a dimethylamino group, a diethylamino group, a dibenzylamino group, a diphenylamino group, a ditolylamino group, and a dianisolylamino group; alkoxyl groups such as a methoxyl group, an ethoxyl group, a propoxyl group, and a phenoxyl group; a cyano group; halogen atoms such as fluorine, chlorine, bromine, and iodine; and the like can be given.

Next, typical examples of the fluorene compound of the present invention will be hereinafter given.

However, the present invention is not limited thereto.

The fluorene compound of the present invention can be synthesized by a well-known method and obtained by using, for example, a synthesis method such as Suzuki coupling method (e.g., Chem. Rev. 1995, 95, 2457-2483) using a palladium catalyst, Yamamoto method (e.g., Bull. Chem. Soc. Jpn. 51, 2091, 1978) using a nickel catalyst, or a method in which a synthesis is performed by using a tin aryl compound (e.g., J. Org. Chem., 52, 4296, 1987).

The fluorene compound of the present invention is superior to the conventional compounds in electron transport property, luminescence property, and durability, which is useful for a layer containing an organic compound of an organic luminescent device, in particular, an electron transport layer and a luminescent layer, and a layer formed by a vacuum evaporation method, a solution-coating method, etc., is hard to undergo crystallization or the like and is excellent in stability with time.

Next, the organic luminescent device of the present invention will be described in detail.

The organic luminescent device of the present invention includes at least a pair of electrodes including an anode and a cathode and one or a plurality of layers containing an organic compound sandwiched between the pair of electrodes, in which at least one of the layers containing the organic compound contains at least one of the fluorene compounds represented by the above general formula [I].

In the organic luminescent device of the present invention, it is preferable that at least an electron transport layer or a luminescent layer among the organic compound-containing layers contain at least one of the fluorene compounds.

In the organic luminescent device of the present invention, the fluorene compound represented by the above general formula [I] is formed between the anode and the cathode by the vacuum evaporation method or the solution-coating method. The organic layer is preferably formed into a thin film with a thickness of less than 10 μm, more preferably 0.5 μm or less, much more preferably 0.01 to 0.5 μm.

Further, according to a preferable mode of the organic luminescent device of the present invention, at least a luminescent layer among the layers containing the organic compound includes at least one of the fluorene compounds represented by the above general formula [I] and one of arylamine compounds represented by the following general formulae [X]to [XIV] and an acetylene compound represented by the following general formula [XV]:

(wherein R 13 and R 14 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, in which R 13 themselves or R 14 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 13 and R 14 which are bonded to the same fluorene group may be identical to or different from each other; R 15 and R 16 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a halogen atom, in which R 15 themselves or R 16 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 15 and R 16 which are bonded to the same fluorene group may be identical to or different from each other; Ar 3 , Ar 4 , Ar 5 , and Ar 6 represent a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted fused polycyclic heterocyclic group, in which Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be identical to or different from one another and Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be bonded with one another to form a ring; and m represents an integer of 1 to 10);

(wherein R 17 and R 18 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, in which R 17 themselves or R 18 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 17 and R 18 which are bonded to the same fluorene group may be identical to or different from each other; R 19 and R 20 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a halogen atom, in which R 19 themselves or R 20 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 19 and R 20 which are bonded to the same fluorene group may be identical to or different from each other; Ar 7 and Ar 8 represent a divalent substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group, in which Ar 7 and Ar 8 may be identical to or different from each other; Ar 9 , Ar 10 , Ar 11 , and Ar 12 represent a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted fused polycyclic heterocyclic group, in which Ar 9 , Ar 10 , Ar 11 , and Ar 12 may be identical to or different from one another and Ar 9 , Ar 10 , Ar 11 , and Ar 12 may be bonded with one another to form a ring; and p represents an integer of 1 to 10);

(wherein R 21 and R 22 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, in which R 21 themselves or R 22 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 21 and R 22 which are bonded to the same fluorene group may be identical to or different from each other; R 23 and R 24 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a halogen atom, in which R 23 themselves or R 24 themselves which are bonded to different fluorene groups may be identical to or different from each other and R 23 and R 24 which are bonded to the same fluorene group may be identical to or different from each other; Ar 13 and Ar 14 represent a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted fused polycyclic heterocyclic group, in which Ar 13 and Ar 14 may be identical to or different from each other and Ar 13 and Ar 14 may be bonded to each other to form a ring; Ar 15 represents a divalent substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group; and q represents an integer of 1 to 10);

(wherein R 25 and R 26 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a halogen atom, in which R 25 themselves or R 26 themselves which are bonded to different phenylene groups may be identical to or different from each other and R 25 and R 26 which are bonded to the same phenylene group may be identical to or different from each other; Ar 16 and Ar 17 represent a divalent substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group, in which Ar 16 and Ar 17 may be identical to or different from each other; Ar 18 , Ar 19 , Ar 20 , and Ar 21 represent a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted fused polycyclic heterocyclic group, in which Ar 18 , Ar 19 , Ar 20 , and Ar 21 may be identical to or different from one another and Ar 18 , Ar 19 , Ar 20 , and Ar 21 may be bonded with one another to form a ring; and r represents an integer of 1 to 10);

(wherein R 27 and R 28 represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, or a halogen atom, in which R 27 themselves or R 28 themselves which are bonded to different phenylene groups may be identical to or different from each other and R 27 and R 28 which are bonded to the same phenylene group may be identical to or different from each other; Ar 22 and Ar 23 represent a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted fused polycyclic heterocyclic group, in which Ar 22 and Ar 23 may be identical to or different from each other and Ar 22 and Ar 23 may be bonded to each other to form a ring; Ar 24 represents a divalent substituted or unsubstituted aromatic group or a substituted or unsubstituted heterocyclic group; and s represents an integer of 1 to 10); and

(wherein Ar 25 and Ar 26 represent a substituted or unsubstituted aromatic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted fused polycyclic aromatic group, or a substituted or unsubstituted fused polycyclic heterocyclic group, in which Ar 25 and Ar 26 may be identical to or different from each other; and t represents an integer of 1 to 5.)

Specific examples of substituents in the general formulae [X] to [XV] are the same as those exemplified in the above general formulae [I] to [IX]. Typical examples of the arylamine compounds represented by the general formulae [X] to [XIV] and the acetylene compound represented by the general formula [XV] will be given below, but the present invention is not limited thereto.

In FIGS. 1 to 6 , preferable examples of the organic luminescent device of the present invention are shown.

FIG. 1 is a cross-sectional view showing an example of the organic luminescent device of the present invention. In FIG. 1 , the device is composed of an anode 2 , a luminescent layer 3 , and a cathode 4 , which are formed on a substrate 1 in order. The luminescent device with this structure is advantageous when the luminescent material used herein has a hole-transporting ability, an electron-transporting ability, and a luminescence property in itself or when plural compounds having the respective characteristics are used as mixed.

FIG. 2 is a cross-sectional view showing another example of the organic luminescent device of the present invention. In FIG. 2 , the device is composed of an anode 2 , a hole transport layer 5 , an electron transport layer 6 , and a cathode 4 , which are formed on a substrate 1 in order. In this case, a luminescent material having either or both of a hole transport property and an electron transport property is advantageously used for the corresponding one of the layers, in combination with a hole transport material or an electron transport material having no luminescence property for the other layer. In addition, in this case, the luminescent layer 3 is composed of either the hole transport layer 5 or the electron transport layer 6 .

FIG. 3 is a cross-sectional view showing still another example of the organic luminescent device of the present invention. In FIG. 3 , the device is composed of an anode 2 , a hole transport layer 5 , a luminescent layer 3 , an electron transport layer 6 , and a cathode 4 , which are formed on a substrate 1 in order. With this arrangement, a carrier transport function and a luminescence function are separated from each other, and plural compounds respectively having a hole transport property, an electron transport property, and a luminescence property are used appropriately in combination therewith. Thus, the degree of freedom upon selecting materials extremely increases. In addition, various kinds of compounds having different luminous wavelengths can be used. Therefore, a variety of luminescence hues can be achieved. Furthermore, it also becomes possible to increase the luminous efficiency by effectively confining each carrier or exciton in the middle luminescent layer 3 .

FIG. 4 is a cross-sectional view showing still another example of the organic luminescent device of the present invention. In FIG. 4 , as compared with the example of FIG. 3 , the device is constructed such that a hole injecting layer 7 is inserted on the anode 2 side. It is effective for improving an adhesion between the anode 2 and the hole transport layer 5 or improving a hole injection property. Thus, this arrangement is effective for lowering a voltage.

FIGS. 5 and 6 are cross-sectional views showing other examples of the organic luminescent device of the present invention, respectively. In FIGS. 5 and 6 , as compared with the examples of FIGS. 3 and 4 , the device is constructed such that a layer (a hole-blocking layer 8 ) serving to prevent a hole or an exciton from passing toward the cathode 4 side is inserted between the luminescent layer 3 and the electron transport layer 6 . The use of a compound having an extremely high ionization potential for the hole-blocking layer 8 is effective for improving the luminous efficiency.

Note that, in FIGS. 1 to 6 , there are shown common basic device structures. The structure of the organic luminescent device using the compound of the present invention is not limited thereto. For example, it is possible to adopt various layer structures such as one in which an insulating layer is formed at the interface between an electrode and an organic layer, one in which an adhesive layer or an interference layer is formed, and one in which the hole transport layer is composed of two layers with different ionization potentials.

The fluorene compound represented by the general formula [I] to be used in the present invention is a compound superior to the conventional compounds in electron transport property, luminescence property, and durability, and the fluorene compound can be used in any of the modes shown in FIGS. 1 to 6 .

In the present invention, the fluorene compound represented by the general formula [I] is used as a component for the electron transport layer or the luminescent layer. However, hole transport compounds, luminescent compounds, electron transport compounds, or other such well-known compounds may be used together as needed.

Examples of those compounds will be given below. Hole transport compound:

Electron Transport Luminescent Material:

Luminescent Material:

Luminescent Layer Matrix Material and Electron Transport Material:

Polymeric Hole Transport Material:

Polymeric Luminescent Material and Charge Transport Material:

In the organic luminescent device of the present invention, the layer containing the fluorene compound represented by the general formula [I] and the layer containing other organic compounds are generally formed as thin films by a vacuum evaporation method or by a coating method after being dissolved in an appropriate solvent. In particular, in the case of forming a film with the coating method, the film formation may be performed in combination with an appropriate binder resin.

The above binder resin can be selected from a wide variety of binder resins including, for example, poly(vinylcarbazole) resin, polycarbonate resin, polyester resin, polyarylate resin, polystyrene resin, acrylic resin, methacrylic resin, butyral resin, poly(vinyl acetal) resin, diallyl phthalate resin, phenolic resin, epoxy resin, silicone resin, polysulfone resin, and urea resin, although not limited thereto. In addition, one of the above resins may be used solely, or two or more such resins may be combined with each other as a copolymer.

Preferably, the anode material may have a work function that is as large as possible. For example, a simple metal substance such as gold, platinum, nickel, palladium, cobalt, selenium, or vanadium, or an alloy thereof, or a metal oxide such as tin oxide, zinc oxide, indium tin oxide (ITO), or indium zinc oxide can be used. In addition, a conductive polymer such as polyaniline, polypyrrole, polythiophene, or poly(phenylene sulfide) can be also used. Any one of those electrode materials may be used solely or the plural electrode materials may be used in combination.

On the other hand, preferably, the cathode material may have a small work function. For example, a simple metal substance such as lithium, sodium, potassium, cesium, calcium, magnesium, aluminum, indium, silver, lead, tin, or chromium, or an alloy of the plural substances can be used therefor. It is also possible to use a metal oxide such as indium tin oxide (ITO). In addition, the cathode may take either a single-layer structure or a multi-layer structure.

The substrate used in the present invention may be, although not particularly limited, an untransparent substrate such as a metallic substrate or a ceramic substrate, or a transparent substrate formed of glass, quartz, plastic sheet, or the like. In addition, it is also possible to control the luminescent color by using a color filter film, a fluorescent color-converting filter film, a dielectric reflection film, or the like for the substrate.

Furthermore, a protective layer or a sealing layer may be also formed on the prepared device for preventing the device from contacting oxygen, moisture, or the like. The protective layer may be a diamond thin film, a film made of an inorganic material such as a metal oxide or a metal nitride, or a polymer film made of fluoroplastics, poly(paraxylylene), polyethylene, silicone resin, polystyrene resin, or the like. In addition, a photo-curing resin or the like can be used therefor. Furthermore, it is also possible to package the device itself with an appropriate sealing resin while covering with glass, a gas-impermeable film, a metal, or the like.

Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to those examples.

Synthesis Example 1

Synthesis of Exemplified Compound No. 1

To a 500-ml three-neck flask, 2.0 g (5.68 mmol) of 2,7-dibromo-9,9-dimethylfluorene [1], 4.2 g (17.0 mmol) of pyrene-1-boronic acid [2], 120 ml of toluene, and 60 ml of ethanol were added. Then, an aqueous solution of 24 g of sodium carbonate/120 ml of water was dropped thereinto with stirring in a nitrogen atmosphere at a room temperature, followed by the addition of 0.33 g (0.28 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at a room temperature, the temperature was allowed to rise to 77° C., followed by stirring for 5 hours. After the reaction, an organic layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane+toluene mixture developing solvent). Consequently, 3.0 g (89% yield) of an exemplified compound No. 1 (white crystal) was obtained.

Synthesis Example 2

Synthesis of Exemplified Compound No. 6

To a 500-ml three-neck flask, 3.0 g (5.49 mmol) of dibromofluorene compound [3], 4.0 g (16.5 mmol) of pyrene-1-boronic acid [2], 100 ml of toluene, and 50 ml of ethanol were added. Then, an aqueous solution of 20 g of sodium carbonate/100 ml of water was dropped thereinto with stirring in a nitrogen atmosphere at a room temperature, followed by the addition of 0.33 g (0.28 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at a room temperature, the temperature was allowed to rise to 77° C., followed by stirring for 5 hours. After the reaction, an organic layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane+toluene mixture developing solvent). Consequently, 3.4 g (79% yield) of an exemplified compound No. 6 (white crystal) was obtained.

Synthesis Example 3

Synthesis of Exemplified Compound No. 7

To a 500-ml three-neck flask, 3.0 g (4.07 mmol) of dibromofluorene compound [4], 3.0 g (12.2 mmol) of pyrene-1-boronic acid [2], 100 ml of toluene, and 50 ml of ethanol were added. Then, an aqueous solution of 16 g of sodium carbonate/80 ml of water was dropped thereinto with stirring in a nitrogen atmosphere at a room temperature, followed by the addition of 0.23 g (0.20 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at a room temperature, the temperature was allowed to rise to 77° C., followed by stirring for 5 hours. After the reaction, an organic layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane+toluene mixture developing solvent). Consequently, 2.7 g (68% yield) of an exemplified compound No. 7 (white crystal) was obtained.

Synthesis Example 4

Synthesis of Exemplified Compound No. 28

To a 500-ml three-neck flask, 3.0 g (6.74 mmol) of diborate fluorene [5], 6.7 g (20.2 mmol) of 3-bromoperylene [6], 140 ml of toluene, and 70 ml of ethanol were added. Then, an aqueous solution of 26 g of sodium carbonate/130 ml of water was dropped thereinto with stirring at a room temperature in a nitrogen atmosphere, followed by the addition of 0.39 g (0.34 mmol) of tetrakis (triphenylphosphine) palladium (0). After stirring the mixture for 30 minutes at a room temperature, the temperature was allowed to rise to 77° C., followed by stirring for 10 hours. After the reaction, an organic layer was extracted with chloroform and was then dried with anhydrous sodium sulfate, followed by purification with a silica gel column (hexane+toluene mixture developing solvent). Consequently, 3.1 g (66% yield) of an exemplified compound No. 28 (white crystal) was obtained.