JP2002356473A - Viologen derivative having chemical structure close to liquid crystal compound, applicable as el element having electron transport property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a viologen derivative and method of production for the same, having principal skeleton close to a liquid crystal compound, polymerizable and useful as an EL element having an excellent electron transport property capable of expecting the electron transport property. SOLUTION: This viologen derivative is expressed by general formula (I) and the invention discloses the method of producing the same. (R<1> is a 1-22C linear or branched chain alkylene group, R<2> is H or methyl group, B is an alkylene group, a -C6 H6 -(CH2 )n -, a -CO-O-(CH2 )n or -CO-, X<1> and X<2> are each a halogen atom.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel viologen derivative which has the same basic skeleton as a liquid crystal compound useful as an organic electroluminescent material, can be polymerized, and can be expected to have excellent electron transport properties, and a method for producing the same. It is about.

[0002]

2. Description of the Related Art Inorganic electroluminescent elements using an inorganic phosphor as a light emitting material are used in, for example, a planar light source as a backlight or a display device such as a flat panel display. Exchange was needed. In recent years, Tang et al. Have an organic electroluminescent device having a double structure in which an organic fluorescent dye is used as a light emitting layer and an organic charge transporting compound used for an electrophotographic photoreceptor or the like (hereinafter referred to as “organic EL device”). ") (Japanese Patent Laid-Open No. 59-194393).
No.). Organic EL devices, compared to inorganic electroluminescent devices, have the feature that low-voltage driving, high luminance, and easy emission of many colors can be easily obtained.Therefore, regarding the device structure, organic fluorescent dye, and organic charge transport compound, Numerous compounds have been proposed.

This organic EL device has a structure in which an organic light emitting layer is sandwiched between two electrodes, and holes injected from an anode and electrons injected from a cathode are recombined in the light emitting layer to emit light. . There are two types of organic EL devices. One is a device in which a fluorescent dye disclosed by CW Tang et al. Is added to a charge transport layer (J. Appl. Phy).
s., 65, 3610.1989) and the other uses a fluorescent dye alone (Jpn. J. Appl. Phys., 27, L269, 1988).
In the latter device, the luminous efficiency is improved when a hole transporting layer that transports only holes, which is one of the charges, and / or an electron transporting layer that transports only electrons is laminated on the fluorescent dye. It is known. As the hole transporting material used for the organic EL device, although various kinds of materials are known, mainly a triphenylamine derivative, there have been few proposals regarding an electron transporting material.

[0004] Examples of electron transport materials proposed so far include, for example, metal complexes of oxine derivatives (Japanese Patent Application Laid-Open No.
No. 9-194393), compounds having a plurality of oxadiazole rings (JP-A-06-145658, JP-A-06-92947, JP-A-05-152072, JP-A-05-202011, 06-
136359), quinoxaline derivatives (Japanese Unexamined Patent Publication No.
6-207169) and the like have been proposed.

[0005]

However, conventionally proposed organic EL devices using these compounds are:
It is not yet sufficient in terms of luminance, life, and luminous efficiency. Accordingly, an object of the present invention is to provide a novel viologen derivative which has a basic skeleton similar to that of a liquid crystal compound, is useful as an organic EL material that can be polymerized, and is expected to have excellent electron transport properties, and a method for producing the same. is there.

[0006]

In the present invention, as a result of intensive studies on a novel compound useful as an organic EL material, the viologen derivative represented by the general formula (1) emits blue light. None, and the basic structure has a tricyclic viologen-based conjugate core, and the conjugated system in this core is a conjugated system with two positive charges and low electron density, so that excellent electron transport properties can be expected. The present invention has been completed.

That is, the first invention of the present invention provides the following general formula (1)

Embedded image (Wherein, R ¹ is a linear or branched alkyl group having 1 to 22 carbon atoms, R ² is a hydrogen atom or a methyl group, A is an alkylene group, —C ₆ H ₆ —CH ₂ —, —CO -O- (CH ₂₎ n
— Or —CO—, X ¹ and X ² represent a halogen atom. )
And a viologen derivative represented by the formula:

Further, a second invention of the present invention provides the following general formula (2)

Embedded image 4,4'-p- (phenylenebisvinylene) represented by
Bipyridine and the following general formula (3)

Embedded image (Wherein R ² , A and X ¹ have the same meanings as defined above) by reacting with a halide represented by the following general formula (4)

Embedded image (R ² , A, and X ¹ have the same meanings as described above.) After obtaining a pyridinium derivative represented by the following general formula (4), the resulting pyridinium derivative represented by the following general formula (5)

Embedded image (Wherein, R ¹ and X ² have the same meanings as described above), and are reacted with an alkyl halide represented by the following general formula (1):

Embedded image (Wherein, R ¹ , R ² , A, X ¹ , and X ² have the same meanings as described above).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the formula of the viologen derivative represented by the general formula (1) of the present invention (hereinafter referred to as compound (1)), R ¹ is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a decyl group A straight-chain or branched alkyl group having 1 to 22 carbon atoms such as a group, a dodecyl group, and an octadecyl group. R
² represents a hydrogen atom or a methyl group. A is an alkylene _{group, -C 6 H 4 -CH 2 -} , - at CO-O- (CH ₂₎ n- or -CO-, a group represented by the alkylene group may be either linear or branched . Specifically, the alkylene group preferably has 1 to 18 carbon atoms, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, an ethylethylene group, a propylene group, a butylene group, and a hexylene group. Octadecylene group, nonylene group, decylene group, dodecylene group and the like. Further, n of —CO—O— (CH ₂ ) n— is 1 to 1.
8 is particularly preferred.

The compounds of the present invention in (1), X ¹ and X ² represents Cl, Br, a halogen atom I arsenide, X ¹
And X ² may be the same or different.

Next, a method for producing the compound (1) will be described. The production method of the present invention basically comprises the following second step.

<First Step> In the first step, the following reaction formula (A) is used.

Embedded image (Wherein R ² , A and X ¹ have the same meanings as described above). This is a step of producing a pyridinium derivative represented by the general formula (4).

The 4,4′-p- (phenylenebisvinylene) bipyridine represented by the general formula (2) as a raw material used in the first step can be produced by a known method. If the following reaction formula (B)

Embedded image There is a reaction represented by

That is, the raw material represented by the general formula (2)
4′-p- (phenylenebisvinylene) bipyridine is
4-picoline (general formula (6)), terephthalaldehyde (general formula (5)), and acetic anhydride (general formula (7)) in a molar ratio of usually 8: 2: 4 under a nitrogen atmosphere at 140 ° C. The reaction can be carried out easily under reflux for about 60 hours.

[0015] The halide represented by the general formula (3), which is the other raw material used in the first step, can be produced by a known method. C)

Embedded image (Wherein, R ² and A have the same meanings as described above; X ¹ represents a halogen atom.) And an alcohol (general formula (8)) and a phosphorus halide (general formula (9)) Is reacted in an equimolar amount in the presence of a base such as pyridine in a solvent such as benzene at 20 ° C. for about 18 hours to easily produce the desired halide represented by the general formula (3). be able to. In addition, such a reaction is preferably performed in the presence of a polymerization inhibitor such as phenothiazine. For example, 4-vinylbenzyl chloride is commercially available from Tokyo Chemical Industry.

X ¹ in the formulas (3) and (9) in the first step is a halogen atom such as chlorine, bromine and iodine.

In the reaction of the first step, the 4,4'-p- (phenylenebisvinylene) bipyridine represented by the general formula (2) and the halide represented by the general formula (3) are dissolved in a solvent. Reaction in

4,4'-p represented by the above general formula (2)
The amount of-(phenylenebisvinylene) bipyridine added is
For the halide represented by the general formula (3),
It is 1.01 times or more, preferably 1.1 to 1.3 times. Examples of the reaction solvent include one or more of ethers such as dioxane, tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone and water. Used in The reaction temperature is not particularly limited, but the reaction is preferably performed under reflux. For example, when dimethylformamide is used as a reaction solvent, a temperature of about 110 ° C. is sufficient. The reaction time is 5 hours or more, preferably 50 to 80 hours.

After completion of the reaction, the pyridinium derivative represented by the general formula (4) is obtained through various operations such as extraction, washing, purification by column chromatography, and further purification such as extraction and dehydration.

<Second Step> The second step is performed according to the following reaction formula (D).

Embedded image (Wherein R ¹ , X ¹ , R ² , X ² , and A have the same meanings as described above).

The reaction in the second step is preferably carried out in a reaction solvent. Examples of the reaction solvent include ethers such as dioxane, tetrahydrofuran and dibutyl ether; nitriles such as acetonitrile and propionitrile; methanol; One or more of alcohols such as ethanol, dimethylformamide, acetone, water and the like are used.

4,4'-p represented by the above general formula (4)
The molar ratio between-(phenylenebisvinylene) bipyridine and the alkyl halide represented by the general formula (5) is:
It is usually 1 to 10, preferably 4 to 6, based on 4,4′-p- (phenylenebisvinylene) bipyridine 1.
The reaction temperature is usually 50 to 200 ° C, preferably 100 to 200 ° C.
At 150 ° C., the reaction time is 5 hours or more, preferably 50 to
80 hours.

After the reaction, the viologen derivative represented by the above general formula (1) is obtained through various purification operations such as recrystallization and washing.

The compound (1) thus obtained is a novel compound useful as an organic EL material, emits blue light, and has a tricyclic viologen-based conjugate core in its basic structure. Is a conjugated system having two positive charges and a low electron density, so that it can be expected to have excellent electron transporting properties.

Further, it has the same chemical structure as the liquid crystal compound represented by the general formula (1) of the present invention, and has an electron transporting EL.
The viologen derivative applicable as an element can of course use the compound (1) as a monomer as an electron transporting material, but the compound (1) has a polymerizable group. Thus, for example, a compound (1) is used by adding a compound (1) to a homopolymer, a copolymer, a polymer compound cross-linked by a cross-linking agent, or a polymer compound having a hydrosilyl group, of the compound (1). You can also.

That is, at least the following general formula (10) or the following general formula (11)

Embedded image

Embedded image (In the formula, R ¹ , R ² , A, X ¹ and X ² have the same meanings as described above.)

The copolymer component of the polymer compound may have a repeating unit derived from acrylic acid, methacrylic acid, styrene or the like. In the case of a copolymer,
The repeating unit represented by the above general formula (10) or (11) accounts for at least 50 mol%, preferably 7
It is 0 mol% or more, more preferably 80 mol% or more.
These polymers have a number average molecular weight of 1,000 to 1,000.
It is in the range of tens of millions, preferably in the range of tens of thousands to millions.

These polymers can be produced by the following method. For example, a homopolymer of the compound (1),
In order to produce a copolymer or a high molecular weight compound cross-linked by a cross-linking agent, a desired monomer or a desired monomer and a cross-linking agent are prepared by a solution polymerization method or a suspension polymerization method in the presence of a polymerization initiator. It can be easily produced by conducting a polymerization reaction by a radical polymerization method such as an emulsion polymerization method and a bulk polymerization method. In addition, in order to produce a high molecular weight compound obtained by subjecting the polymer compound having a hydrosilyl group to an addition reaction with the compound (1), the polymer compound having a hydrosilyl group and the compound (1) are converted into chloroplatinic acid, Alcohol solution of chloroplatinic acid, platinum-olefin complex, platinum-based catalyst such as platinum-vinylsiloxane complex, Wilkinson complex,
It can be easily produced by conducting the reaction in the presence of a rhodium-based catalyst such as a complex of rhodium and carbonyl.

The compound (1) of the present invention or a polymer compound containing the compound (1) can be used as a composition containing the compound. Such a composition contains at least 30% by weight or more, preferably 5% by weight of compound (1).
It is preferable that the composition contains 0% by weight or more, more preferably 80% by weight or more. Other components in the composition include a liquid crystal compound exhibiting a smectic phase or a nematic phase. Such a composition is prepared by dissolving a compound (1) or a polymer compound containing the compound (1) and a desired component described above in a solvent, and then heating and melting the solvent, or sputtering, vacuum deposition, or the like. Can be prepared.

Compound (1) of the present invention, Compound (1)
It is particularly preferable to use a polymer compound containing the compound or a composition containing the same by utilizing molecular orientation in a liquid crystal state. That is, the compound (1), a polymer compound containing the compound (1), or a composition thereof is a lyotropic liquid crystal (concentration transition type liquid crystal) obtained by dissolving the compound (1) in a solvent capable of dissolving the compound at a high concentration. State, it is preferable to use in a state in which the solvent is removed while maintaining the molecular orientation of the lyotropic liquid crystal state, and a composition with a liquid crystal compound showing a smectic phase or a nematic phase, the smectic phase or nematic phase It is preferable to use it in a liquid crystal state or in a solid state generated by a phase transition in a process of lowering the temperature from the smectic phase, specifically, a crystalline phase, a glassy state, or an amorphous solid.

Compound (1) of the present invention, Compound (1)
The compound (1) has a tricyclic viologen-based conjugate core in its basic structure, and the conjugated system of this core portion has two positive charges. Since it is a conjugated system having a low electron density, excellent electron transport properties can be expected. For example, an organic EL element in which an anode, a hole transport layer, a light emitting layer, and a cathode are sequentially stacked, or an anode, a light emitting layer, and an electron In an organic EL device in which a transport layer and a cathode are sequentially stacked, at least a compound (1) of the present invention, a polymer compound containing the compound (1), or a light-emitting layer, an electron transport layer, and a hole transport layer; These compositions are coated on an electrode surface such as ITO by spin coating, L
The organic EL element is immobilized by the B method, the dip method, or the like, and is used as an organic EL element while maintaining the molecular orientation of a liquid crystal state as described above, for example, as an electron transporting layer or a hole transporting layer. It can be expected that the brightness, the life, and the luminous efficiency will be obtained. That is, as shown in FIG. 1, a conventional electron transport mechanism using an organic compound is a hopping mechanism in which the transfer of electrons in an organic compound is performed by randomly transferring electrons between adjacent molecules. When the compound (1) of the present invention is used as a composition with, for example, a compound having a smectic phase, and the composition is used in a liquid crystal state of a smectic phase, the composition has a layered arrangement as shown in FIG. In such a state, electron transfer is performed in a state where the conjugate portion of the compound overlaps with the nectar, so that efficient electron transport can be performed.

[0032]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 3 <Synthesis of 10-bromo-1-decene as a starting material used in the first step> 15.6 g (0.1 mol) of 10-decene-1-ol and 0.8 g of pyridine (0. 01 mol) and 0.1 g of phenothiazine were dissolved in 100 ml of dry benzene.
Next, 100 ml of a benzene solution in which 27.0 g (0.1 mol) of phosphorus tribromide was dissolved was slowly dropped under ice-cooling.
Stir at room temperature for 18 hours. Thereafter, the reaction solution was poured into ice water and extracted with 300 ml of diethyl ether. The ether-benzene mixture obtained here was dehydrated with anhydrous sodium sulfate overnight. Next, sodium sulfate was removed by suction filtration, ether-benzene was removed under reduced pressure, and the residue was distilled under reduced pressure to obtain 8.1 g of 9-bromo-1-decene (yield: 43.3%).

<Identification data> Distillation temperature: 69 to 75 ° C. (1 mmHg) FT-IR (KBr, cm ⁻¹ ): 3010 (alkene CH stretching vibration), 285
4-2927 (CH stretching vibration), 1641 (C = C stretching vibration), 1456
(CH in-plane deflection), 647 to 669 (CH out-of-plane deflection) ¹ H-NMR (δ, CDCl ₃ ): 1.0 to 2.2 (m, 14 H,-(CH ₂ ) ₇
−), 3.3 to 3.5 (d, 2H, Br—CH ₂ ), 4.8 to 5.2 (d, 2
H, CH ₂ = CH-), 5.5 to 6.2 (m, 1H, -C = C)

<4,4'-p- of the raw material used in the first step
Synthesis of (phenylenebisvinylene) bipyridine> 7.46 g (80 mmol) of 4-picoline and 2.68 g (20 mmol) of terephthalaldehyde were added to 4.08 (40) of acetic anhydride.
mmol) and reacted at 140 ° C. for 60 hours under a nitrogen atmosphere. After cooling to 80 ° C., hot water was poured and stirred.
After cooling to room temperature, the deposited dark brown precipitate was separated by filtration and washed with water until the washing solution reached pH 7. The resulting precipitate is adjusted to pH
The mixture was added to an aqueous solution of sodium carbonate 10 and stirred for 24 hours. This was extracted with chloroform, the solution was concentrated and reprecipitated with diethyl ether. Next, the precipitate was dissolved in ethanol, ethanol was removed under reduced pressure to remove insoluble components,
By reprecipitation with chloroform-hexane, 2.89 g (yield: 45.1%) of the desired product was obtained.

<Identification data> Melting point: 264 to 267 ° C. FT-IR (KBr, cm ^-1 ): 3023 to 2918 (aromatic CH stretching), 1591 (C = C ring stretching), 1504 (C = N Ring expansion and contraction), 831 (C
-H surface outside ^{bending) · 1 H-NMR (δ} , DMSO-d6): 7.0~7.3 (d, 4H, -CH
= CH-), 7.4 (d, 4H, aromatic), 7.6 (s, 4H), 8.
6 (d, 4H) ・ Elemental analysis Theoretical value: C 84.47%, H 5.67%, N 9.85%, C / N 8.58% Measurement value: C 84.14%, H 5.92%, N 9.94%, C / N 8.46% MS spectrum; M ⁺ = 284

First Step <Synthesis of Pyridinium Derivative> 4,4 ′ prepared above
-P- (phenylenebisvinylene) bipyridine 0.71
g (2.5 mmol) and 10-bromo-1 prepared above
-0.44 g (2.0 mmol) of decene was dissolved in 10 ml of DMF in an ampoule. The tube was sealed, reacted at 110 ° C. for 72 hours, filtered, and DMF was removed under reduced pressure.
Next, the resultant was washed several times with diethyl ether, and subjected to column chromatography (Wakogel C-300, 40 g, MeOH: C
HCl ₃ = 1: 20) and the purified product was dissolved in a small amount of methanol and extracted with water. Next, the precipitate was collected by a centrifugal separator, and after removing water under reduced pressure, the precipitate was dissolved in 150 ml of chloroform and dehydrated with anhydrous sodium sulfate.
After filtration, chloroform was removed under reduced pressure, washed with diethyl ether and dried to obtain 0.08 g (yield: 8%) of the target product, a pyridinium derivative represented by the following general formula (12).

Embedded image In addition, the number in General formula (12) shows the position of the assignment of H in ¹ H-NMR.

<Identification data> FT-IR (KBr, cm ^-1 ): 2925 (CH stretching) 2854 (Alken CH
Stretching), 1620-1710 (C = C, C = N ring stretching), 1466 (CH bending angle), 858 (CH out-of-plane bending angle) ¹ H-NMR (δ, DMSO-d6): 1.5 to 2.1 ( m, 14H,-
_{(CH 2) 7 -),} 4.6~4.7 (t, 2H, 5), 5.0~5.1
(M, 2H, 7), 5.8-5.9 (m, 1H, 6), 8.0-8.3
(M, 12H, 1,2, aromatic, -CH = CH-), 8.4 (d, 2H,
4), 9.1 to 9.2 (d, 2H, 3) Elemental analysis Theoretical values: C 71.56%, H 7.01%, N 5.57%, C / N 12.85
% Measured value: C 72.28%, H 7.05%, N 5.92%, C / N 12.22
%

Second step <Synthesis of viologen derivative> 0.037 g (0.0073 mmol) of the pyridinium derivative obtained in the first step was added to 1
It was dissolved in DMF of 0 ml, then represented by the general formula C _n H _{2n + 1} Br 1- bromo alkane 0.07g (n = 8,0.365m
Mol), 0.08 g (n = 10, 0.365 mmol),
0.09 g (n = 12, 0.365 mmol) was gradually added dropwise. After reacting at 110 ° C. for 70 hours in a nitrogen atmosphere, the reaction solution is concentrated and recrystallized with acetonitrile, and then the precipitate is washed with diethyl ether to obtain a viologen derivative represented by the following general formula (13). Got each.

Embedded image In addition, the numerical value in general formula (13) shows the position of the assignment of H in ¹ H-NMR.

<Compound of general formula (13) where n = 8> Yield 0.037 g, 72.5% Further, ¹ H-NMR (DMSO-d6) analysis data as identification data is shown in Table 1 as FT-NMR. Table 2 shows the analysis data of IR (KBr).

[0041]

[Table 1]

[0042]

[Table 2]

[0043] <Formula (13) compounds of n = 10 in> Yield 0.043 g, 81.4% yield also a ^{1 H-NMR (DMSO-d6} ) analytical data as identification data in Table 3 FT- Table 4 shows the analysis data of IR (KBr). FIG. 3 shows a fluorescence spectrum at an excitation wavelength of 387 nm.

[0044]

[Table 3]

[0045]

[Table 4]

<Compound with n = 12 in General Formula (13)> Yield 0.022 g, 39.4% Yield ¹ H-NMR (DMSO-d6) analysis data as identification data in Table 5 Table 6 shows the analysis data of IR (KBr).

[0047]

[Table 5]

[0048]

[Table 6]

Examples 4 to 5 First Step <Synthesis of Pyridium Derivative> 0.71 g (2.5 mmol) of 4,4'-p- (phenylenebisvinylene) bipyridine prepared in the same manner as in Examples 1 to 3 ) Was dissolved in 10 ml of DMF. To this, 4-vinylbenzyl chloride 0.2
5 ml of 7 g (1.75 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.)
The solution dissolved in DMF was gradually added dropwise. After reacting at 70 ° C. for 24 hours in a nitrogen atmosphere, the reaction solution was concentrated and extracted with water. This aqueous solution was removed under reduced pressure to remove water, and washed with diethyl ether to obtain 0.16 g of a pyridinium derivative represented by the following general formula (14) (yield: 20.8 g).
6%).

Embedded image In addition, the numerical value in general formula (14) shows the position of the assignment of H in ¹ H-NMR.

<Identification data> FT-IR (KBr, cm ^-1 ): 3037 (aromatic CH stretching), 2920
(Aliphatic CH stretching), 1407-1616 (C = C, C = N ring stretching), 8
33 (CH out-of-plane bending angle) ¹ H-NMR (δ, DMSO-d6): 9.1 to 9.2 (d, 2H,
3), 8.7-8.8 (d, 2H, 1), 8.3 (d, 2H, 4),
7.5 to 8.0 (m, 14H, 2, aromatic, -CH = CH-), 6.8
(M, 1H, -CH = C), 5.8 (s, 2H, N ⁺ -CH _2- ), 5.
3,6.0 (d, 2H, -C = CH 2) · Elemental analysis Theoretical value; C 79.70%, H 5.77% , N 6.41%, C / N 12.43
% Measured value: C 76.54%, H 5.98%, N 6.15%, C / N 12.45
%

Second Step <Synthesis of Viologen Derivative> Pyridi obtained in the first step
Is dissolved in 5 ml of DMF, then the general formula C_nH _{2n + 1}
0.13 g of 1-chloroalkane represented by Cl (n = 1
0, 0.75 mmol), 0.15 g (n = 12, 0.7
(5 mmol) was gradually added dropwise. Under nitrogen atmosphere,
After reacting at 110 ° C. for 75 hours, the reaction solution was concentrated,
Recrystallize each with acetonitrile, then precipitate the precipitate.
After washing with tyl ether, a bifunctional resin represented by the following general formula (15)
Orogen derivatives were obtained respectively.

Embedded image The numerical value in the formula of the general formula (15) indicates the position of the assignment of H in ¹ H-NMR.

<Compound with n = 10 in General Formula (15)> Yield 0.03 g, 25.9% ¹ H-NMR (DMSO-D6) analysis data as identification data is shown in Table 7 as FT-NMR data. Table 8 shows the analysis data of IR (KBr).

[0053]

[Table 7]

[0054]

[Table 8]

[0055] <Formula (15) compounds of n = 12 in> Yield 0.07 g, 58.3% yield also a ^{1 H-NMR (DMSO-D6} ) analytical data as identification data in Table 9 FT- Table 10 shows the analysis data of IR (KBr). FIG. 4 shows a fluorescence spectrum at an excitation wavelength of 387 nm.

[0056]

[Table 9]

[0057]

[Table 10]

[0058]

As described above, the viologen derivative of the present invention represented by the general formula (1) has a basic skeleton similar to a liquid crystal compound, can be polymerized, and can be expected to have excellent electron transport properties. And it is expected to be used as an organic EL material.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a mechanism of electron transport ability of a conventional organic compound.

FIG. 2 shows an electron when a mixture of a viologen derivative having a chemical structure similar to that of the liquid crystal compound of the present invention and applicable as an electron transporting EL device and a liquid crystal compound having a smectic phase is used in a smectic liquid crystal state. FIG. 3 is a schematic diagram showing a transport mechanism.

FIG. 3 shows n = 1 in the general formula (13) obtained in Examples.
The figure which shows the fluorescence spectrum at the excitation wavelength of 387 nm of the compound of No. 0.

FIG. 4 shows n = 1 in the general formula (15) obtained in Examples.
The figure which shows the fluorescence spectrum at the excitation wavelength of 387 nm of the compound of No. 2.

Continued on the front page F term (reference) 3K007 AB00 AB02 AB03 BB01 CA01 CB01 DA00 DB03 EB00 FA01 FA02 4C055 AA04 BA01 CA01 DA27 DB02 EA01 FA03 GA01 4J100 AQ11P BC43P CA01 DA66 JA32

Claims (2)

[Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ is a linear or branched alkyl group having 1 to 22 carbon atoms, R ² is a hydrogen atom or a methyl group, A is an alkylene group, —C ₆ H ₆ —CH ₂ —, —CO -O- (CH ₂₎ n
— Or —CO—, X ¹ and X ² represent a halogen atom. )
A viologen derivative represented by the formula: 2. The following general formula (2): 4,4'-p- (phenylenebisvinylene) represented by
Bipyridine and the following general formula (3) (Wherein R ² , A and X ¹ have the same meanings as defined above) by reacting with a halide represented by the following general formula (4): (R ² , A, and X ¹ have the same meanings as described above.) After obtaining a pyridinium derivative represented by the following general formula (4), the resulting pyridinium derivative represented by the following general formula (4): Formula 5 Wherein R ¹ and X ² have the same meanings as defined above, and are reacted with an alkyl halide represented by the following general formula (1): (Wherein, R ¹ , R ² , A, X ¹ , and X ² have the same meanings as described above).