JP3397247B2 - New metal complex liquid crystal - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel metal complex liquid crystal compound useful as an optical display material or an optical recording material, and more particularly, as a charge transport material for a liquid crystal device, a molecular element or an electrophotographic photoreceptor. .

[0002]

Organometallic complexes are generally useful as catalysts or pigments. It is known from the following documents that when this complex exhibits a liquid crystal phase, it can be expected to exhibit new physicochemical properties.

(1) Chem. Ber., 59,962 (1926) (2) Liquid. Cryst., 1,215 (1986) (3) Mol, Cryst. Liq. Cryst., 13,305 (1971) (4) Mol, Cryst. Liq. Cryst., 20,133 (1973) (5) Mol, Cryst. Liq. Cryst., Lett, 34,117 (1976) (6) J. Chem. Soc., Chem. Commun., 1980,797 (7) Mol. Cryst. Liq. Cryst., 43,53 (1977) (8) JCS Chem., Chommun, 1986,581 (9) Mol. Cryst. Liq. Cryst., 84,207 (1982) (10) S. Chandrasekjar, BKSadashiva and BSSrikan
ta, preprint (11) Khim. Teknol. Krasheniya, Sint. Krasitelei po
lim. mater., 1981,60 (12) Dokl. Akad. Nauk SSSR, 276,126 (1984) (13) Mol. Crust. Liq. Cryst., 123,369 (1985) Organometallic compounds exhibiting a liquid crystal phase described in the above document. The complexes are listed below.

[0004]

[Chemical 2]

[0005]

[Chemical 3]

[0006]

[Chemical 4]

[0007]

[Chemical 5]

[0008]

[Chemical 6]

[0009]

However, many of the above-mentioned conventional metal complex liquid crystal compounds are easily thermally decomposed at the clearing point, and it is possible to obtain a chemically stable liquid crystal device by using this compound. It was difficult. Moreover,
Discotics useful as one-dimensional organic conductive materials
Very few columnar liquid crystal phases were exhibited, which was the reason why a charge transfer complex composed of only discotic liquid crystal could not be prepared.

An object of the present invention is to provide a metal complex having a discotic columnar liquid crystal phase and having an electron donating property and being thermally stable.

[0011]

The present invention has the general formula (I) for solving the above-mentioned problems.

[0012]

[Chemical 7]

(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, preferably a linear alkyl group having 1 to 20 carbon atoms, and M represents a transition metal). A compound is provided.

Further, there is provided a discotic columnar liquid crystal composition containing a compound represented by the general formula (I).

The compounds of general formula (I) according to the present invention are
For example, it can be manufactured according to the following manufacturing method.

[0016]

[Chemical 8]

(In the above, R represents the same meaning as R in formula (I).) First step: A mixture of the compound of formula (II) and bismuth oxide is dissolved in glacial acetic acid and heated to reflux. . The reaction mixture is extracted with a chlorine-based solvent such as chloroform, the extract is washed with water and dried, and then the solvent is distilled off. Next, the obtained residue can be purified by silica gel chromatography to produce a compound of general formula (III).

Second step: NH ₂ OH.HCl and potassium hydroxide are added to ethanol, and the mixture is vigorously stirred and then filtered. The compound of general formula (III) produced in the first step is added to this filtrate, and the mixture is refluxed under a nitrogen stream. After adding a methanol solution of a divalent metal salt such as palladium chloride or nickel chloride to this, the reaction solution is neutralized with acetic acid and further refluxed. After cooling, the reaction solution is filtered, the filtrate is column purified, and then recrystallized from acetone to produce the compound of the general formula (I) according to the present invention. Table 1 shows the phase transition temperatures of typical compounds represented by the general formula (I) thus produced.

[0019]

[Table 1]

(In the table, C represents a crystalline phase, D represents a discotic phase, and I represents an isotropic liquid phase.) The compound of the general formula (I) of the present invention was observed by a polarizing microscope in a liquid crystal phase. By X-ray structural analysis, discotic columnar liquid crystal phase, more specifically, Dhd phase (Discotic hexagonal diso
It was revealed that the electron-donating metal complex has a rdered columnar phase. Therefore, it can be understood that it is useful as a charge transport material for an electrophotographic photoreceptor.

[0021]

The present invention will be further described below by showing Examples of the present invention. However, the invention is not limited to these examples.

The structure of the compound was confirmed by NMR and IR. CDCl _{3 in} NMR represents a solvent, t represents a triplet, and m represents a multiplet. (KBr) in IR represents the measurement by tableting.

(Example 1-a) Formula (A) in a nitrogen atmosphere

[0024]

[Chemical 9]

A mixture of 2.5 g (4.55 mmol) of the compound of 2.5 and 2.55 g (5.47 mmol) of bismuth oxide was heated to reflux in 20 ml of glacial acetic acid for 10 hours. After completion of the reaction, the reaction product was extracted with chloroform, the extract was dried with Na ₂ SO ₄ , and the solvent was distilled off. The obtained product is subjected to silica gel column chromatography (benzene, Rf = 0.88).
Purified using the formula (B) in the form of a yellow syrup.

[0026]

[Chemical 10]

1.41 g of the compound of Yield 57% ¹ H-NMR (CDCl ₃ ) δ (ppm): 0.88 (t, 12H),
1.32 (m, 32H), 2.63 (t, 8H), 7.03 to 7.70 (m, 6
H)

The Erlenmeyer flask (Example _{1-b) 500ml, NH 2} OH · HCl7.12g (0.10 mol), 85% KOH7.12g (0.10
Mol) and 175 ml of ethanol were added, and the mixture was vigorously stirred for 1 hour. After completion of the reaction, the precipitated KCl was filtered off and 0.95 g of the compound of formula (B) obtained in (Example 1-a) was added to the filtrate.
(1.73 mmol) was added, and the mixture was refluxed for 6 hours under a nitrogen stream. Palladium chloride dissolved in 5 ml of ethanol
After adding 0.13 g (0.74 mmol), the reaction solution was neutralized with acetic acid. After cooling the reaction mixture to room temperature, the dark green precipitate that formed was filtered off. The precipitate was dried and then purified using silica gel chromatography (carbon tetrachloride: benzene = 1: 1, Rf = 0.66), and then recrystallized from acetone to purify the compound below.
18g was obtained. This compound was also thermally stable.

[0029]

[Chemical 11]

Yield 17% Transition temperature 123 ℃ (C → D) 146 ° C (D → I)

[0031]

INDUSTRIAL APPLICABILITY The compound of the general formula (I) of the present invention is a metal complex liquid crystal having a discotic columnar liquid crystal phase, having an electron donating property and thermally stable, and useful as a one-dimensional organic conductive substance. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-255363 (JP, A) JP-A-4-120048 (JP, A) JP-A-51-125435 (JP, A) Z. Natureforsch. , 1979, 34b, P245-250 (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 251/70 C07C 49/782 C07F 15/00 C09K 19/40 G02F 1/13 500 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A compound represented by the general formula (I): (In the formula, R represents an alkyl group having 1 to 20 carbon atoms, and M represents a transition metal). 2. The compound according to claim 1, wherein M is palladium. 3. A discotic columnar liquid crystal composition containing the compound represented by the general formula (I) according to claim 1.