JPH0674244B2 - Novel TCNQ complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has a novel structure of TCNQ useful as a conductive material and the like.
It relates to a (7,7,8,8-tetracyanoquinodimethane) 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 the advantage that it can utilize the characteristic properties of organic compounds as a metal, such as light weight, electrical conductivity anisotropy, meltability, film formability, and ease of processing and molding. , 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, a large number of nitrogen-containing heterocyclic compound cation TCNQ complexes have been synthesized so far, but they are all produced by either of the following two methods. That is, one of them is a method of utilizing the reducibility of iodo ion I ⁻ to react a synthetic nitrogen heterocyclic compound cation iodide D ⁺ I ⁻ with neutral TCNQ in the presence of a suitable solvent such as acetonitrile or dichloromethane. , The other is to react the same cation D ⁺ halide with TCNQ Li salt in a solvent such as methanol. Is obtained in a solvent such as acetonitrile.
This is a method of doping TCNQ.

However, these conventional methods known per se can only obtain the TCNQ complex having the most stable structure in the solvent used, and therefore, the cation (D ⁺ ) And TCNQ anion radical And the neutral TCNQ (TCNQ °) composition ratio is determined by the nitrogen-containing heterocyclic compound used and the solvent used, and TCNQ complexes with various composition ratios can be produced depending on the purpose. It is extremely impossible, and therefore TCNQ having a special complex composition ratio other than the complex composition ratio obtained by the usual method.
The complex has never existed before.

[Object of the Invention]

An object of the present invention is to provide a novel TCNQ complex having a special complex constituent ratio, which can be expected to have new possibilities in various semiconductor fields.

[Structure of Invention]

The present invention includes one or more cations (D ⁺ ) of a nitrogen-containing heterocyclic compound selected from the group consisting of
8,8-Tetracyanoquinodimethane anion radical And a neutral TCNQ (TCNQ ゜) (In the formula, m represents a number such that 0 <m <1 or 1 <m ≦ 3.5. However, when D ⁺ is N-n-propylquinolinium cation, it is excluded when m = 0.9.) TCNQ complex shown.

That is, the present inventors have found that the nitrogen-containing heterocyclic compound (D ⁺ ) and TCNQ
Anion radical TCNQ complex consisting of and TCNQ (TCNQ °) However, it cannot be obtained by the conventional method. As a result of intensive studies to obtain TCNQ complexes having various complex constituent ratios with various values of m, a mixture of any combination described in (i) to (v) below was heated without a solvent. The inventors have found that the object can be achieved by a melting reaction, and completed the present invention.

(I) Cation (D ⁺ ) of nitrogen-containing heterocyclic compound and 7,7,8,8
-Tetracyanoquinodimethane anion radical TCNQ simple salt consisting of One or two or more of which may be different from each other, and TCNQ
(7,7,8,8-Tetracyanoquinodimethane).

(Ii) Cations (D ⁺ ) of nitrogen-containing heterocyclic compounds and 7,7,8,8
-Tetracyanoquinodimethane anion radical And TCNQ complex salt composed of neutral TCNQ (TCNQ ゜) 1 type or 2 or more types which may be different from each other, and TCN
Q.

(Iii) TCNQ simple salt One or two or more of which may be different from each other, and TCNQ
complex salt 1 type or 2 or more types which may be different from each other, and TCN
Q.

(Iv) TCNQ complex salt 2 or more that may be different from each other.

(V) TCNQ simple salt One or two or more of which may be different from each other, and TCNQ
One kind of complex salt or two or more kinds which may be different from each other.

The novel TCNQ complex of the present invention is In normal conducted by known per se and the method as preparation of TCNQ complexes represented, i.e., iodide ion I ^- of using the reductive nitrogen-containing heterocyclic compound cation iodides D ⁺ I ^- and neutral
A method in which TCNQ is reacted in the presence of a suitable solvent such as acetonitrile or dichloromethane, or a halide of the same cation D ⁺ and a Li salt of TCNQ are reacted in a solvent such as methanol. Is obtained in a solvent such as acetonitrile.
No matter how the TCNQ is doped, it is impossible to obtain the neutral TCNQ even if the amount of the neutral TCNQ is increased or decreased.

Specific examples of the novel TCNQ complex of the present invention are as follows.

(0 <n <1 (where n ≠ 0.9) or 1 <n ≦ 3.5) (0 <n <1 or 1 <n ≦ 3.5) (0 <n <1 or 1 <n ≦ 3.5) (0 <n <1 or 1 <n ≦ 3.5) (0 <n <1 or 1 <n ≦ 3.5) The TCNQ single salt used in the production of the novel TCNQ complex of the present invention can be easily obtained by heating the halide of the nitrogen-containing heterocyclic compound cation and the Li salt of TCNQ in a solvent such as methanol. It is sufficient to use the one obtained in.

Further, the TCNQ complex used in the production of the novel TCNQ complex of the present invention utilizes the reducibility of the iodo ion I ⁻ , and the molar ratio of the nitrogen-containing heterocyclic compound cation iodide D ⁺ I ⁻ and neutral TCNQ is 3: 4.
Or a halide of the same cation D ⁺
React with TCNQ Li salt The compound obtained by a method known per se, such as a method of doping the same with neutral TCNQ, can be used without exception.

According to the method for producing a novel TCNQ complex of the present invention, which comprises subjecting a mixture of any of the combinations (i) to (v) to a heat-melting reaction, a compound of the formula In the TCNQ complex represented by, any of m having an arbitrary value in the range of 0 <m ≦ 3.5 can be produced.

That is, for example, if 1 <m ≦ 3.5 is desired, this can be obtained by subjecting a mixture consisting of the combination of the above (i), (ii) or (iii) to a heating and melting reaction in the absence of a solvent. , If 0 <m ≦ 1 is desired,
Usually, the desired complex can be easily obtained by the same treatment as above using a mixture consisting of the combination of (i) or (v). When the mixture consisting of the combination of the above (iv) is used, 0 <m ≦ 1 can be prepared or 1 <m ≦ 3.5 can be prepared depending on the kind of TCNQ complex salt used and the combination thereof. You can also

Of the present invention (However, m is a number such that 0 <m <1 or 1 <m ≦ 3.5)
CNQ complex is applied to high-performance conductive molecular films, non-linear optical materials, antistatic agents, molecular devices, biodevices, the design of highly ordered molecular assemblies with electronic functions, or the solid state of electrolytic capacitors and batteries. There are great expectations for its use in various organic semiconductor fields such as electrolytes.

Reference examples and examples are shown below, but the present invention is not limited to these reference examples and examples.

〔Example〕

Reference example 1. Synthesis of TCNQ single salt (1) Synthesis of TCNQ lithium salt TCNQ 20.4 g (0.1 mol) was dissolved in acetonitrile 1.5 with heating, and lithium iodide 26.8 g (0.2 m
ol) was dissolved in 200 ml of acetonitrile, and the solution was refluxed for 1 hour. After the reaction, the reaction mixture was cooled to collect crystals and dried to obtain 20.0 g of purple powder crystals. Yield 94.8
%.

(2) Iodide of nitrogen-containing heterocyclic compound cation (N
-Synthesis of alkyl quaternary ammonium iodide) An equimolar amount of an organic base and an alkyl iodide are mixed with or without a solvent in a suitable organic solvent, and the boiling point of the solvent is 13
The reaction was carried out at 0 ° C for 0.5 to 10 hours. After the reaction, the mixture was cooled and the precipitated crystals were taken and recrystallized with an appropriate solvent. The results are shown in Table 1.
Shown in.

(3) Synthesis of TCNQ single salt 4.22 g (20 mmol) of lithium salt of TCNQ obtained in (1) was dissolved in 175 ml of methanol with heating, and 20 mmol of iodide of nitrogen-containing heterocyclic compound cation was added to methanol.
A solution dissolved in 50 ml was added dropwise and the mixture was refluxed for 1 hour.
After the reaction, the mixture was cooled to collect crystals, which were recrystallized from acetonitrile to obtain TCNQ single salt. The results are shown in Table 2.

The specific resistance values in the table are 25 ° C after molding the sample powder into pellets.
The current value was measured by the two-terminal method, the resistance value R was calculated, and the resistance value R was calculated from the following equation.

ρ = R · A / l where 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 endothermic point and exothermic decomposition point were determined by differential scanning calorimetry (DSC) measurement.

Reference Example 2. Synthesis of TCNQ Complex 3.06 g (15 mmol) of TCNQ was dissolved in 150 ml of acetonitrile under heating, and the N-alkyl fourth compound obtained in Reference Example 1- (2) was added thereto.
An acetonitrile solution in which a quaternary ammonium iodide (11.25 mmol) was dissolved was added dropwise and refluxed for 1 hour.
After cooling, the precipitated crystal was taken and recrystallized from acetonitrile to obtain a TCNQ complex. Table 3 shows the physical properties of the obtained TCNQ complex.

In the table, neutral TCNQ (denoted as TCNQ °) and anion radical TC
NQ Complex composition ratio of (A. Rembaum etc., J. Am. Chem. Soc., 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 14 TCNQ Single Salt Reaction with TCNQ In a container of Al (or pt) having high thermal conductivity, Nn-butylisoquinolinium TCNQ single salt 3.9 g (0.01 mol) and TCNQ 4.08 g.
(0.02 mol) was sufficiently pulverized and mixed, and the mixture was heated and reacted at 240 ° C. for 1 minute. After the reaction, the container was rapidly cooled, the solidified crystals were taken out, and the target TCNQ complex was obtained as a black-purple powder. Got The specific resistance value (ρ value) of the obtained complex is 10 Ω · cm.
(Two-terminal method).

In addition, this product was recrystallized from acetonitrile to obtain black purple needle crystals. The specific resistance of the recrystallized product is 9Ω ・ cm, Was 1.95.

If the amount of TCNQ added is changed by the same operation, another TC
Table 4 shows the results when NQ single salt was used and when experiments were performed using a plurality of TCNQ single salts.

Comparative Example 1 N-n-butylisoquinolinium iodide 3.13 g
(0.01 mol) and 4.08 g (0.02 mol) of TCNQ were refluxed in 200 ml of acetonitrile for 1 hour and then allowed to stand at room temperature for crystallization to precipitate yellow crystals and black-purple short needle crystals. As a result of separating and analyzing each, the yellow crystal was TCNQ and the black purple short needle crystal was It was a TCNQ complex of 1.0.

Examples 15 to 21 Reaction of TCNQ complex with TCNQ and reaction between TCNQ complexes Nn-butylisoquinolinium TCNQ complex was placed in a container of Al (or Pt) having high thermal conductivity. 2.97 g (0.005 mol) and TCNQ1.02 g (0.005 mol) were sufficiently pulverized and mixed, and the mixture was heated and reacted at 240 ° C. for 1 minute. After the reaction, the container was rapidly cooled and the solidified crystals were taken out to obtain the target TCNQ complex as a black-purple powder. Got

The specific resistance value of this product was 15 Ω · cm.

This product was recrystallized from acetonitrile to give black purple needle crystals. The specific resistance value of the recrystallized product is 12 Ω ・ cm, Was 1.91.

If the TCNQ addition amount is changed by the same operation, other TCNQ
Table 5 shows the results when the complex was used and when an experiment was further performed using a plurality of TCNQ complexes.

Examples 22 to 25 Reaction of TCNQ Single Salt with TCNQ Complex 1,2-Dimethyl-in a container of Al (or Pt) having high thermal conductivity
3-n-butyl-1H-imidazolium single salt 1.79 g (0.005
Mol) and 1,2-dimethyl-3-n-butyl-1H-imidazolium complex 2.81g (0.005mol) is thoroughly crushed and mixed, then 220 ℃
The mixture was heated and reacted for 1 minute. After the reaction, the container was rapidly cooled, and the solidified crystals were taken out to give the desired TCNQ complex as a black-purple powder. Got The specific resistance value of this product was 30 Ω · cm. The product was recrystallized from acetonitrile to obtain black purple plate crystals. The specific resistance of the recrystallized product is 25 Ω ・ cm, Was 0.45.

Hereinafter, the same operation was performed using Nn-butylisoquinolinium single salt and its complex, and the results in Table 6 were obtained.

[Advantages of the Invention] As described above, the present invention provides a nitrogen-containing heterocyclic compound (D ⁺ )
And TCNQ anion radical TCNQ complex consisting of and TCNQ (TCNQ °) The present invention provides a novel TCNQ complex having an unprecedented value of m, that is, an unprecedented complex composition ratio, and has an unprecedented new possibility in various semiconductor fields. It can be expected.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location H01B 1/12 B 7244-5G (72) Inventor Mamoru Nagoya 1633 Matagoba Kawagoe City Saitama Prefecture Wako Jun Yakuhin Kogyo Co., Ltd., Tokyo Laboratory (56) References JP-A-61-118904 (JP, A) J. Am. Chem. Soc. , 84 (1962-9-5) p. 3374-3387

Claims (1)

[Claims] 1. A cation (D ⁺ ) of one or more nitrogen-containing heterocyclic compounds selected from the group consisting of:
7,8,8-Tetracyanoquinodimethane anion radical And a neutral TCNQ (TCNQ ゜) (In the formula, m represents a number such that 0 <m <1 or 1 <m ≦ 3.5. However, when D ⁺ is Nn-propylquinolinium cation, it is excluded when m = 0.9.) TCNQ complex shown.