JPH0684350B2 - New TCNQ complex - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel TCNQ complex useful as a conductive material and the like.

[Background of the Invention]

The TCNQ complex is a charge-transfer complex compound known as an organic semiconductor, and its constituent component TCNQ easily accepts an electron, and forms an extremely stable radical salt with a cation.
It exhibits high conductivity due to its own structural feature of stacking itself.

The TCNQ complex has the advantages that it has the characteristic properties of an organic compound and the properties of a metal, such as light weight, electrical conductivity anisotropy, meltability, film formability, and ease of processing and molding. Therefore, high-performance conductive molecular film, nonlinear optical material,
There are great expectations for its application in applications to antistatic agents, molecular devices, biological devices, the design of highly ordered molecular assemblies with electronic functions, or in various organic semiconductor fields such as solid electrolytes for electrolytic capacitors and batteries. Is a compound.

Regarding the TCNQ complex, many nitrogen-containing heterocyclic compound cation TCNQ complexes have been synthesized so far, but the TCNQ complex is an organic compound by nature, and the structure and the structure of the TCNQ complex are gradually changed by changing the substituents and constituent elements. Since it is possible to change the properties, it is possible to optimize various properties required as a conductor according to the purpose.
Development of NQ complex is desired.

[Object of the Invention]

The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel TCNQ complex which is an organic conductive compound and can be expected to have various electrochemical or photochemical results.

[Constitution of Invention] The present invention has the formula [Wherein R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a cyano group, a hydroxyl group, a trifluoromethyl group or a fluorine atom, and R ² represents an alkyl group having 1 to 8 carbon atoms or-(CH ₂ ) _m OCH ₃ group (provided that m is an integer of 2 to 5). ] 1-substituted-4- [2-phenyl (or substituted phenyl) ethenyl] pyridinium cation represented by
7,7,8,8-Tetracyanoquinodimethane anion radical And a TCNQ complex containing neutral TCNQ (TCNQ °) as a constituent component.

The TCNQ complex of the present invention is represented, for example, as follows.

(In the formula, x represents an arbitrary number of 0.5 ≦ x ≦ 2.0.) In the TCNQ complex of the present invention, the formula of the donor part 4- [2-phenyl (or substituted phenyl) represented by
R ¹ of the ethenyl] pyridinium cation is a hydrogen atom, for example, a lower alkyl group such as a methyl group, an ethyl group and a propyl group, for example, a lower alkoxy group such as a methoxy group and an ethoxy group, a nitro group, a cyano group, a hydroxyl group, trifluoromethyl Represents a group or a fluorine atom, and R ² is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, or the like, and has a straight chain or a branched chain having 1 to 8 carbon atoms An alkyl group having, for example, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxyamyl group, and the like, a methoxyalkyl group represented by the formula — (CH ₂ ) _m OCH ₃ group (provided that m is an integer of 2 to 5). Show.

The TCNQ complex of the present invention utilizes 1-substituted-4- [2-phenyl (or substituted phenyl) ethenyl] pyridinium iodide by utilizing a method known per se, for example, the reducing property of iodo ion I ^−. It can be easily obtained by a method of reacting with neutral TCNQ at a molar ratio of 3: 4. 1-substituted-4- [2-phenyl (or substituted phenyl) ethenyl] pyridinium iodide, for example, J.Org.Chem., 28, 387 ( 1963), J.Org.Che
m., 21 , 1039 (1956), J.Chem.Soc., 1960 , 1516, J.Chem.
Soc., 1934 , 276, etc., γ-picoline is reacted with benzaldehyde or a substituted benzaldehyde in acetic anhydride to obtain 4- [2-phenyl (or substituted phenyl) ethenyl] pyridine, which is then required. Since it can be easily obtained by reacting with alkyl iodide or methoxyalkyl iodide in the presence of a suitable solvent, it is sufficient to use the thus obtained product. Methoxyalkyl iodides are prepared, for example, by synthesizing methoxyalkyl chlorides from alkyl chlorides and metal methylates according to the method described in J. Am. Chem. Soc., 72 , 1334 (1950), etc. Since it can be easily obtained by reacting with an alkali in a suitable solvent with heating, the product thus obtained may be used.

Further, the TCNQ complex of the present invention is obtained by reacting a halide of 1-substituted-4- [2-phenyl (or substituted phenyl) ethenyl] pyridinium cation with a Li salt of TCNQ. It is needless to say that the same can be obtained by the method in which the compound is obtained and is doped with neutral TCNQ.

The synthesized TCNQ complex of the present invention can be identified by the color unique to the charge transfer complex and the appearance of the charge transfer absorption band,
The complex composition ratio can be determined from elemental analysis and ultraviolet absorption spectrum measurement. The electrical property, for example, the specific resistance value, can be obtained from the following equation by molding the sample powder into pellets, measuring the current / voltage by the two-terminal method to calculate the resistance value R. ρ = R · A / l. However, ρ is the specific resistance value (Ω · cm),
R is the resistance (Ω), A is the electrode contact area (cm ² ), and 1 is the sample thickness (cm). The thermal property can be measured by thermal analysis such as differential scanning calorimetry (DSC) measurement.

The novel TCNQ complex of the present invention is particularly excellent in conductivity, processing and moldability of a single product or a mixture product thereof, and therefore, it can be used as a highly functional conductive molecular film, a non-linear optical material, or a molecular element thereof,
It can be expected to be effectively used in various organic semiconductor fields such as the design of highly ordered molecular assemblies having electronic functions such as application to biological devices, or as a solid electrolyte for electrolytic capacitors and batteries.

Examples and Reference Examples are shown below, but the present invention is not limited by these Examples and Reference Examples.

〔Example〕

Reference Example 1. Synthesis of 4- (2-phenylethenyl) pyridine γ-picoline 9.3 g (0.1 mol), benzaldehyde 10.6 g
(0.1mol) and acetic anhydride 10.2g (0.1mol)
Reflux reaction was performed for 0 hours. Next, 200 ml of water was added, and the mixture was concentrated under reduced pressure, cooled, and the precipitated crystals were collected, washed with water and alcohol, and dried to obtain 16.5 g of crude crystals. This was recrystallized from ethanol to obtain 6.5 g of pale yellowish brown scaly crystals of 4- (2-phenylethenyl) pyridine (yield 35.9%).

mp 127-128 ° C.

Reference Examples 2 to 10. In the same manner as in Reference Example 1 using 9 kinds of substituted benzaldehydes, 9 kinds of 4- (2-substituted phenylethenyl) pyridines were obtained. The results are shown in Table 1.

Example 1. Synthesis of 1-n-butyl-4- (2-phenylethenyl) pyridinium TCNQ complex (1) 1-n-butyl-4- (2-phenylethenyl)
Synthesis of pyridinium iodide 4- (2-phenylethenyl) pyridine obtained in Reference Example 1
3.6 g (20 mmol) of n-butyl iodide in ethanol 3.7 g
The mixture was refluxed for 1.5 hours. Next, the reaction solution is concentrated under reduced pressure, the residue is crystallized from acetone and ethanol, and the precipitated crystals are collected and recrystallized from acetone-ethanol to give 1-
4.0 g of yellow powdery crystals of n-butyl-4- (2-phenylethenyl) pyridinium iodide were obtained (yield 55.1).
%). mp 183-185 ° C.

Elemental analysis (C ₁₇ H ₂₀ IN) theory (%) C: 55.90, H : 5.52, N: 3.83 Found (%) C: 55.72, H : 5.61, N: 3.86.

(2) Synthesis of TCNQ complex 3.06 g (15 mmol) of 7,7,8,8-tetracyanoquinodimethane was dissolved in 150 ml of acetonitrile with heating, and 1-n-butyl-4 obtained in (1) was added to the solution. A solution of 4.0 g of-(2-phenylethenyl) pyridinium iodide in acetonitrile was added dropwise and the mixture was refluxed for 1 hour. The reaction solution was cooled and the precipitated crystals were collected and recrystallized from acetonitrile to give 1-
4.1 g of black-violet prism crystals of n-butyl-4- (2-phenylethenyl) pyridinium TCNQ complex were obtained (yield 84.6).
%). Elemental analysis value (C ₄₁ H ₂₈ N ₉ ) Theoretical value (%) C: 76.14, H: 4.36, N: 19.49 Actual value (%) C: 76.02, H: 4.52, N: 19.46.

Specific resistance value: 27 Ω · cm.

DSC: endothermic point 253 ° C; exothermic decomposition point 270 ° C.

Examples 2-20 Synthesis of 1-substituted-4- (2-substituted phenylethenyl) pyridinium TCNQ complex (1) Synthesis of 1-substituted-4- (2-substituted phenylethenyl) pyridinium iodide Reference Examples 1-10 19 kinds of 1-substituted-4- (2-substituted phenyl) were obtained in the same manner as in (1) of Example 1 by using 10 kinds of 4- (2-substituted phenylethenyl) pyridines obtained in 1. and various alkyl iodides. Ethenyl) pyridinium iodide was obtained. The results are shown in Tables 2 (1) to (4).

(2) Synthesis of TCNQ complex 19 kinds of 1-substituted-4- (2-substituted phenylethenyl) pyridinium iodides obtained in (1) were used in the same manner as in (2) of Example 1 to obtain 19 kinds. The TCNQ complex of was obtained. The results are shown in Tables 3 (1) to (3).

In addition, neutral TCNQ (displayed as TCNQ °) and anion radical TCNQ Complex composition ratio with (A. Rembaum et al., J. Am. Chem. Soc., 93 , 2532 (1
971)) according to the ultraviolet absorption spectrum measurement method. The endothermic point and exothermic decomposition point were determined by differential scanning calorimetry (DSC) measurement. Regarding the electrical characteristic value, the complex was made into pellets, and the current-voltage measurement (two-terminal method) was performed at 25 ° C after sample preparation according to the usual method below, and the specific resistance value ρ (Ω · cm) was calculated based on the above calculation formula. It was

〔The invention's effect〕

As described above, the present invention is characterized by using a 1-substituted-4- [2-phenyl (or substituted phenyl) ethenyl] pyridinium cation, which has not been used in the TCNQ complex, as a donor. A new TC that can be expected to have various electrochemical or optical results that have not existed before
The present invention has a remarkable effect in that it can provide an NQ complex, and is a great invention in contributing to the art.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C07D 213/57 // H01B 1/12 B 7244-5G

Claims (1)

[Claims] 1. A formula [Wherein R ¹ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a cyano group, a hydroxyl group, a trifluoromethyl group or a fluorine atom, and R ² represents an alkyl group having 1 to 8 carbon atoms or-(CH ₂ ) _m OCH ₃ group (provided that m is an integer of 2 to 5). ] 1-substituted-4- [2-phenyl (or substituted phenyl) ethenyl] pyridinium cation represented by
7,7,8,8-Tetracyanoquinodimethane anion radical And a TCNQ complex containing neutral TCNQ (TCNQ °) as a constituent component.