JPH0730023B2 - Method for producing organic conductive complex - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a novel organic conductive complex. More specifically, the present invention provides a novel organic conductive material having a donor part composed of two or more different nitrogen-containing heterocyclic compound cations and an acceptor part composed of TCNQ or a derivative thereof (substituted TCNQ) as constituents. It relates to a method for producing a complex.

[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 electrons and forms a radical salt that is extremely stable with cations.
It shows high conductivity due to the structural characteristics of NQ itself being uniquely stacked.

The TCNQ complex has advantages that it can utilize the characteristic properties of organic compounds as a metal, such as light weight, electrical conductivity anisotropy, meltability, film formability, processing and molding acceptability. Therefore, high-performance conductive molecular film, nonlinear optical material,
It is a compound that is expected to be used in various organic semiconductor fields such as application to molecular devices and biological devices, design of highly ordered molecular assemblies having electronic functions, or solid electrolytes of electrolytic capacitors and batteries. .

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 the properties can be changed, it is possible to optimize various properties required as an electric conductor according to the purpose, which can meet various needs.
Development of TCNQ complex is desired.

[Object of the Invention]

The present invention has been made in view of the present situation as described above, is an organic conductive compound, various electrochemical, or a method for producing a TCNQ complex or a substituted TCNQ complex having a novel structure that can be expected to have photoelectrochemical results. Its purpose is to provide.

[Structure of Invention]

The present invention provides a cation iodide of two or more different nitrogen-containing heterocyclic compounds, and a compound of the formula [I] (Wherein R and R ′ each independently represent hydrogen or a lower alkyl group) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) or a derivative thereof (substituted TCNQ). At the ratio of the latter mole number 4 to the total mole number 3 of the former, TCNQ or substitution with each nitrogen-containing heterocyclic compound cation
After heating for a certain period of time in an organic solvent in which any of the complexes consisting of TCNQ and is soluble and at least one of the complexes can be recrystallized, crystals of the reaction product are formed in the same solvent. A method for producing an organic conductive complex comprising a donor part composed of two or more different nitrogen-containing heterocyclic compound cations and an acceptor part composed of TCNQ or a substituted TCNQ, which are characterized in that they are prepared by precipitation. Is the invention of.

In the method for producing the novel conductive complex of the present invention, the lower alkyl group represented by R and R'of TCNQ represented by the formula [I] or its derivative (substituted TCNQ) is, for example, methyl group, ethyl group,
Examples thereof include lower alkyl groups such as propyl group and butyl group.

Examples of the nitrogen-containing heterocyclic compound cation used in the method for producing the novel conductive complex of the present invention include isoquinoline derivatives, quinoline derivatives, pyridine derivatives, picoline derivatives, pyridazine derivatives, pyrazine derivatives, pyrimidine derivatives, 1,10- Phenanthroline derivative, benzimidazole derivative, benzothiazole derivative, imidazole derivative, thiazole derivative, morpholine derivative, pyrazole derivative, diazabicyclo [2,2,2] octane derivative, hexamethylenetetramine derivative, 4-phenylpyridine derivative, 4-styrylpyridine derivative And other cations.

The nitrogen-containing heterocyclic compound cations are represented by the following general formulas, respectively.

Isoquinoline derivative Quinoline derivative Pyridine derivative Picoline derivative Pyridazine derivative Pyrazine derivative Pyrimidine derivative 1,10-phenanthroline derivative Benzimidazole derivative Benzothiazole derivative Imidazole derivative Thiazole derivative Morpholine derivative Pyrazole derivative Diazabicyclo [2,2,2] octane derivative Hexamethylenetetramine derivative 4-phenylpyridine derivative 4-styrylpyridine derivative (However, all of R ^{1 to} R ¹⁸ in the general formulas in the above ^{1 to 4} represent an alkyl group having 1 to 22 carbon atoms, an allyl group or an aralkyl group, and X ^{1 to} X ^{4 in} are methyl. Group, a lower alkyl group such as an ethyl group.) As a solvent used in the method for producing the novel conductive complex of the present invention, a nitrogen-containing heterocyclic compound cation and TCNQ represented by the formula [I] or substituted TCNQ Any of two or more different complexes consisting of and are soluble, and at least one of them is soluble.
Any organic solvent may be used as long as the complex of the species can be recombined. For example, acetonitrile is a typical one and is particularly preferable.

The method for producing the novel conductive complex of the present invention is carried out as follows.

That is, iodide of two or more different nitrogen-containing heterocyclic compound cations and TCNQ or substituted TC represented by the formula [I]
NQ and the latter are in a ratio of 4 moles to the total of 3 moles of the former, and each of the complexes of the nitrogen-containing heterocyclic compound cation and TCNQ or substituted TCNQ is soluble, and After heating and reacting in an organic solvent (for example, acetonitrile or the like) capable of recombining at least one of the complexes therein for a certain period of time, crystals of the reaction product are precipitated in the same solvent.

The complex produced by the method for producing a novel conductive complex of the present invention is a complex in which the donor part is composed of two or more different nitrogen-containing heterocyclic compound cations, but the donor part is a single nitrogen-containing heterocompound. It exhibits the same physical properties as the single complex composed of cations. Such a complex has never been disclosed before and is a complex of a completely new structure, which can only be obtained by the method of the invention.

Hereinafter, the complex obtained by the method of the present invention is referred to as a complex complex.

On the other hand, two or more different complexes are pulverized and mixed at an arbitrary ratio, or two or more different complexes are dissolved in a solvent in which these complexes are easily dissolved, for example, N, N-dimethylformamide. This complex complex cannot be obtained by a method in which different complexes of the above are dissolved by heating and then poured into water for crystallization (Japanese Patent Publication No. Sho 60-11697). Only a mixed complex is obtained.

That is, for example, the present complex complex obtained by the production method of the present invention shows one endothermic point and one exothermic decomposition point in principle by differential scanning calorimetry (DSC) measurement, as in the case of the single complex. Thus, the above mere mixed complex obviously exhibits physical properties as a mixture, and exhibits a plurality of endothermic points or a plurality of exothermic decomposition conversions. Thus, the present complex complex and the mere mixed complex are clearly different in the differential scanning calorimetry (DSC) measurement, which shows that they are completely different types of complexes.

The complex obtained by the method of the present invention is a semiconductor in terms of electrical characteristics in any of the complexes, and the present complex complex obtained in this manner is different from the one obtained by simply mixing the complexes with each other. It is a completely new type of complex that behaves.

The new type TCNQ complex or the substituted TCNQ complex produced by the method of the present invention can be identified by the appearance of a charge transfer complex-specific color or charge transfer absorption band as in the case of a normal TCNQ complex, and the complex composition ratio is determined by elemental analysis. And the ultraviolet absorption spectrum. 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 and voltage by the two-terminal method to calculate the resistance value R, and ρ = R · A / l. Where ρ is the specific resistance value (Ω
・ Cm), R is resistance (Ω), A is electrode contact area (cm ² ),
l is the thickness (cm) of the sample. The thermal properties can be measured by thermal analysis such as differential scanning calorimetry (DSC) measurement.

Examples of the complex complex produced by the method of the present invention include, but are not limited to, the followings.

(2-n-butylisoquinolinium) a (1-n-butylpyridinium) b (7,7,8,8-tetracyanokidimethane) ₂ (2-n-butylisoquinolinium) a (1-n-butylquinolinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (2-n-butylisoquinolinium) a (3-n-butyl-1,2-dimethyl-1H-imidazolium) b (7,7,8,8
-Tetracyanoquinodimethane) ₂ (2-n-butylisoquinolinium) a (4-n-butyl-4-methylmorpholinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (2-n-butylisoquinolinium) a (1-n-propylquinolinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (1-n-butylpyridinium) a (4-n-butyl-
4-methylmorpholinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (1-n-butylpyridinium) a (3-n-butyl-
1,2-dimethyl-1H-imidazolium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (1-n-butylpyridinium) a (1-n-propylquinolinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (1-n-butylpyridinium) a (1-n-butylquinolinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (3-n-butyl-1,2-dimethyl-1H-imidazolium) a (4-n-butyl-4-methylmorpholinium)
b (7,7,8,8-tetracyanoquinodimethane) ₂ (3-n-butyl-1,2-dimethyl-1H-imidazolium) a (1-n-propylquinolinium) b (7,7,8,8
-Tetracyanoquinodimethane) ₂ (3-n-Butyl-1,2-dimethyl-1H-imidazolium) a (1-n-butylquinolinium) b (7,7,8,8-
Tetracyanoquinodimethane) ₂ (4-n-butyl-4-methylmorpholinium) a (1
-N-propylquinolinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (4-n-butyl-4-methylmorpholinium) a (1
-N-butylquinolinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (1-n-butylquinolinium) a (1-n-propylquinolinium) b (7,7,8,8-tetracyanoquinodimethane) ₂ (2-n-butylisoquinolinium) a (4-n-butyl-4-methylmorpholinium) b (2-methyl-7,7,
8,8, -Tetracyanoquinodimethane) ₂ (2-n-Butylisoquinolinium) a (4-n-butyl-4-methylmorpholinium) b (2,5-dimethyl-
7,7,8,8, -Tetracyanoquinodimethane) ₂ (2-n-butylquinolinium) a (1-n-propylquinolinium) b (4-n-butyl-4-methylmorpholinium) c (7,7,8,8-tetracyanoquinodine methane)
_Two (2-n-butylisoquinolinium) a (1-n-butylpyridinium) b (3-n-butyl-1,2-dimethyl-1H-imidazolium) c (7,7,8,8-tetra Cyanoquinodimethane) ₂ (2-n-butylisoquinolinium) a (4-n-butyl-4-methylmorpholinium) b (1-n-propylquinolinylium) c (3-n-butyl-1,2-dimethyl -1H-imidazolium) d (7,7,8,8-tetracyanoquinodimethane) ₂ (2-n-butylisoquinolinium) a (4-n-butyl-4-methylmorpholinium) b (1-n-propylnolinylium) c (1-n-butylpyridinium) d
(3-n-Butyl-1,2-dimethyl-1H-imidazolium) e (7,7,8,8-tetracyanoquinodimethane) ₂ 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 N-alkyl quaternary ammonium iodide (iodide of nitrogen-containing heterocyclic compound cation) Equimolar organic base (nitrogen-containing heterocyclic compound) and alkyl iodide in a solvent-free or appropriate organic solvent Mix with
The reaction was carried out at the boiling point of the solvent to 120 ° C for 15 minutes to 10 hours. After cooling, the reaction solution was treated to obtain a crude N-alkyl quaternary ammonium iodide, which was recrystallized with an appropriate solvent and purified. The physical properties of the obtained N-alkyl quaternary ammonium iodide are shown in Tables 1 (a) and 1 (b).

Reference Example 2 Synthesis of TCNQ complex 3.06 g (15 mmol) of TCNQ was dissolved in 150 ml of acetonitrile under heating, and an acetonitrile solution containing the N-alkyl quaternary ammonium iodide (11.25 mmol) obtained in Reference Example 1 was added dropwise thereto. Then, the mixture was refluxed for 1 hour. After cooling, the precipitated crystals are collected and recrystallized from acetonitrile
An NQ complex was obtained. Table 2 shows the physical properties of the obtained TCNQ complex.
Shown in.

In the table, neutral TCNQ (denoted as TCNQ °) and anion radical TC
NQ ( (Displayed as) complex composition ratio (A. Rembaum etc., J. Am. Chem. Sco., 93 , 2532 (197
It was determined by the method of ultraviolet absorption spectrum measurement according to 1)).
The differential scanning calorific value (DS
C) Obtained by measurement. Regarding the electrical characteristic values, the complex was used as a pellet, and the current-voltage measurement (two-terminal method) was performed at 25 ° C. after the sample was prepared according to the conventional method, and the specific resistance value ρ (Ω · cm) was calculated based on the calculation formula.

Examples 1 to 26 complex TCNQ complex (or complex DMTCNQ complex)
Preparation of TCNQ 3.06g (15mmol) (or DMTC in 150ml of acetonitrile)
NQ3.49 g (15 mmol) was dissolved under heating, and 2 or more kinds of N-alkyl quaternary ammonium iodides obtained in Reference Example 1 (total 11.25 mmol): 2 or more kinds of N-alkyl quaternary 4
The primary ammonium iodide is mixed at an arbitrary ratio, and the total number of moles thereof is 11.25 mmol. ) Was dissolved in acetonitrile solution was added dropwise. After dropping, the mixture was refluxed for 1 hour, cooled, and the precipitated crystals were taken and dried to obtain a composite TCNQ complex (or a composite DMTCNQ complex).

The results are shown in Tables 3 (a) to (f).

The method for measuring physical properties is the same as in Reference Example 2. or,
DSC charts of the complex complexes according to the present invention obtained in Examples 6, 8, 11, 15, 22, 23, 25 and 26 are shown in FIGS. 1 to 8.

Comparative Examples 1-3 Production of mixed TCNQ complex Two or more different TCNQ complexes are mixed at an arbitrary ratio (total:
7.50 mmol) DMF (50 ml) was heated to 80 to 90 ° C. and dissolved, and then the solution was poured into water (5). The crystals precipitated by cooling to 20 ° C. were collected and dried sufficiently to obtain a mixed TCNQ complex.

Table 4 shows the physical properties and the like of the obtained mixed TCNQ complex.

The method for measuring physical properties is the same as in Reference Example 2. or,
DSC charts of the mixed complexes obtained in Comparative Examples 1 and 3 are shown in FIGS. 9 and 10.

Comparative Examples 4,5 Production of mixed TCNQ complex Crystals of two or more different TCNQ complexes were finely pulverized and mixed at an arbitrary ratio to obtain a mixed TCNQ complex.

The DSC charts of the obtained mixed TCNQ complex are shown in Figs. 11 and 12.
Shown in the figure.

However, Comparative Example 4 When And 1: 1 mixed. In addition, Comparative Example 5 as well as Mixed with 1: 1: 1: 1: 1.

〔The invention's effect〕

As described above, the present invention discloses a method for producing a complex complex, which is an organic conductive complex having a completely novel structure, which has never been disclosed so far. Alternatively, it has a remarkable effect in that it can provide a TCNQ complex and a substituted TCNQ complex having a completely new structure and physical properties that can be expected to have photoelectrochemical results.

[Brief description of drawings]

1 to 8 show DSC charts of the complex complexes according to the present invention obtained in Examples 6, 8, 11, 15, 22, 22, 23, 25 and 26, respectively.
9 to 12 are DSC charts of the complex complexes obtained in Comparative Examples 1, 3, 4, and 5, respectively.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C07D 233/58 295/02 Z // H01B 1/12 B H01G 9/028 (72) Inventor Nagoya Mori 1633 Matoba, Kawagoe City, Saitama Prefecture, Tokyo Research Laboratory, Wako Pure Chemical Industries, Ltd. (56) References JP-A-62-467 (JP, A)

Claims (3)

[Claims] 1. An iodide of two or more different nitrogen-containing heterocyclic compound cations and a compound of the formula [I] (Wherein R and R ′ each independently represent hydrogen or a lower alkyl group) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) or a derivative thereof (substituted TCNQ). At the ratio of the latter mole number 4 to the total mole number 3 of the former, TCNQ or substitution with each nitrogen-containing heterocyclic compound cation
After heating for a certain period of time in an organic solvent in which any of the complexes consisting of TCNQ and is soluble and at least one of the complexes can be recrystallized, crystals of the reaction product are formed in the same solvent. A method for producing an organic conductive complex comprising a donor part composed of two or more different nitrogen-containing heterocyclic compound cations and an acceptor part composed of TCNQ or a substituted TCNQ, which are characterized in that they are prepared by precipitation. . 2. The nitrogen-containing heterocyclic compound cation is
The method according to claim 1, which is a cation of a nitrogen-containing heterocyclic compound selected from the group consisting of: Isoquinoline derivative Quinoline derivative Pyridine derivative Pycholine derivative Pyridazine derivative Pyrazine derivative Pyrimidine derivative 1,10-phenanthroline derivative Benzimidazole derivative Benzothiazole derivative Imidazole derivative Thiazole derivative Morpholine derivative Pyrazole derivative Diazabicyclo [2,2,2] octane derivative Hexamethylenetetramine derivative 4- Phenylpyridine derivative 4-styrylpyridine derivative 3. The method according to claim 1 or 2, wherein the solvent is acetonitrile.