JPS63233976A - Novel tcnq complex - Google Patents

Abstract

NEW MATERIAL:A TCNQ complex containing a N-substituted isoquinolinium cation (R<1> is cyclopropyl, cyclopentyl or cyclohexyl; n is 1-3), 7,7,8,8- tetracyanodimethane anion radical (TCNQ<->) and neutral TCNQ as constitutional components. USE:An electroconductive molecular membrane having high function, nonlinear optical material, solid electrolyte for electrolytic capacitor and electric battery, etc. PREPARATION:A halide of N-substituted isoquinolinium cation is reacted with a Li salt of TCNQ to afford a compound expressed by formula II, which is subjected to doping with a neutral TCNQ to provide the aimed product expressed by formula III (0.5<=k<=2.0).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel TCNQ complex useful as a conductive material or the like.

(Background of the invention) TCNQ complex is a charge-transfer type complex compound known as an organic semiconductor, and its component TCNQ easily accepts electrons, forms extremely stable radical salts with cations, and TCNQ itself It exhibits high electrical conductivity due to its unique structural feature of stacked claws.

TCNQ complexes have the advantage of having both the characteristic properties of organic compounds and the properties of metals, such as light weight, anisotropy of conductivity, meltability, film-forming properties, and ease of processing and molding. Therefore, it is useful for applications in high-performance conductive molecular films, nonlinear optical materials, antistatic agents, molecular devices, biological devices, the design of highly ordered molecular aggregates with electronic functions, or solid electrolytes for electrolytic capacitors and batteries. , is a compound that is highly expected to be used in various organic semiconductor fields.

Regarding TCNQ complexes, a large number of desired elements #i
A cationic TCNQ complex of a ring compound has been synthesized,
Originally, TCNQ complex is an organic compound, and its structure and properties can be changed little by little by changing substituents and constituent elements. Since it is possible to measure the TCNQ complex according to the purpose, it is desired to develop a new TCNQ complex that can meet these various needs.

[Purpose of the invention]

The present invention was made in view of the current situation as described above, and an object of the present invention is to provide a novel TCNQ complex, which is an organic conductive compound and is expected to have various electrochemical or photochemical results.

[Structure of the invention]

(However, R1 represents a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, and n represents an integer of 1 to 3.

) an N-substituted quinolinium cation represented by
This is an invention of a TCNQ complex comprising a 7,7,8.8-tetracyanoquinodimethane anion radical (TCNQ) and a neutral TCNQ (TCNQ) as constituent components.

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

(In the formula, k represents an arbitrary number ranging from 0.5≦≦2.0.) In the TCNQ complex of the present invention, R1 of the quinolinium cation of the formula of the donor part is a cyclopropyl group, a cyclopentyl group, group or a cyclohexyl group, and n represents an arbitrary integer of L to 3.

The T CN Q jff body of the present invention can be obtained by a method known per se,
For example, it can be easily synthesized by a method of doping NQ by reacting a halide of an N-substituted quinolinium cation with TCNQ σ, i salt. Since the halo of the N-substituted quinolinium cation can be easily obtained by reacting it with isoquinoline in the presence of a suitable solvent if necessary, it is sufficient to use the product obtained in this way. In addition, the TCNQ complex of the present invention utilizes the reducing power of iodo ion 1- to produce N-substituted isoquinoline 3:4
Needless to say, it can be synthesized in the same manner by a reaction method.

The synthesized TCNQ complex of the present invention can be identified by the appearance of the color and charge transfer absorption band characteristic of charge transfer complexes, and the complex composition ratio can be determined from elemental analysis and measurement of ultraviolet absorption spectra. Electrical properties, for example, specific resistance value, can be determined from the following equation by molding the sample powder into a pellet, measuring the current and voltage using the two-terminal method, and calculating the resistance value R. ρ=R−A/n. However, ρ is the specific resistance value (Ω・cm), R is the resistance (Ω), and A is the electrode contact area (
cm''), iL is the thickness of the sample (cm).
Thermal properties can be measured by thermal analysis such as differential scanning calorimetry (DSC) measurements.

The novel TCNQ complex of the present invention is particularly excellent in electrical conductivity, processing and moldability, and heat resistance when used alone or as a mixture. It is expected that it can be effectively used in various organic semiconductor fields, such as in the design of highly ordered molecular aggregates with electronic functions, such as applications in biological devices, or as solid electrolytes in electrolytic capacitors and batteries.

Examples are shown below, but the present invention is not limited in any way by these examples.

〔Example〕

Reference Example 1. Synthesis of 2-cyclopropylethyl bromide (1) Synthesis of 2-cyclopropylacetonitrile Cyclopropylmethyl bromide (manufactured by Aldrich) 15
g (I11 mmol) was reacted with 6.1 g (124 mmol) of sodium cyanide in DMSO (dimethyl sulfoxide) at 70° C. for 3 hours with stirring, and then poured into water. Next, extraction was performed with ethyl ether, and the ether layer was washed with diluted hydrochloric acid and then with water, followed by anhydrous Mg5O.

It was dried. After drying and removing the residue, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain a fraction 5.
9 g was obtained as a colorless oil (yield 65.6%).

I R (Neat): 2200cm-' (-C
=N).

(2) Synthesis of ethyl 2-cyclopropylacetate 2-cyclopropylacetonitrile obtained in (1) 5.93 (7:
1 mmol) was dissolved in 3.7 g of ethanol and 30 mj of ethyl ether, and the hydrogen chloride gas was dissolved at 10°C or below.
9g was introduced. After introduction! After stirring at 5° C. for 2 hours, the mixture was concentrated under reduced pressure, and water and ether were poured into the residue. After stirring at room temperature for 30 minutes, the ether layer was separated by standing and separated, and washed with water, followed by anhydrous Mg5O.

It was dried. After removing the desiccant, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain a fraction 4. with a BP of 55-57°C/30mmHg. Og
was obtained as a colorless oil (yield: 42.7%).

IR (Neat,): 1730cm-'
(-GO(H:2]15).

(3) Synthesis of 2-cyclopropylethanol An ether solution of 4.0 g (31 mmol) of ethyl 2-cyclopropylacetate obtained in (2) was added dropwise to an ether solution in which 710 mg of LiA was suspended, and then 1 Stirring was performed for hours. After injecting the reaction solution into water, separate the ether layer, concentrate the ether layer, and distill the residue under reduced pressure.
1.5 g of a 65+nmHg fraction was obtained as a colorless oil (yield 66.7%).

I R (Neat): 3300cm-' (-0
11).

(4) Synthesis of 2-cyclopropylethyl bromide (3
) 1.4 g of 2-cyclopropyl ethanol (19
, 4 mmol) was reacted with 2.7 g of phosphorus tribromide in methylene chloride at 0 to 5° C. for 1 hour, and the reaction solution was poured into water and extracted with methylene chloride. Na1lGO methylene chloride layer
, After washing with an aqueous solution and washing with water, it was dried with anhydrous Mg5O. After removing the desiccant, the solvent was distilled off, and the remaining 1 h was distilled to
1.3 g of a fraction of 127-129° C. was obtained as a colorless oil (yield 49.6%).

Reference Example 2. Synthesis of 2-cyclohexylmethylisoquinolinium bromide 74 g (60 mmol) of isoquinoline (manufactured by Wako Pure Chemical Industries, Ltd. After reacting for 4 hours, acetone and ethanol were added and dissolved under reflux.

The reaction solution was cooled, and 5 precipitated crystals were collected, washed, and dried to obtain 7.8 g of pale yellow crystals (yield: 42.4%).

mp　199-203℃.

Elemental analysis value (G+5HzoBrN) Theoretical value C%) C: 62.75. H:6.58.
N: 4.57 actual value (96) C: 62.54. H
:6.79. N: 4.66゜'HN M R
δρρ (CDα3n: 0.52~2.22
(1011゜rn, cyclohexyl-C2
~G,), 1.85~2.45 (III, m.

cyclohexyl-C,), 5.02 (2H, d,
, 1-611z,;N"(If,-).

7.78-9.22 (6H, m, 1soquinol
ine-C3~C,l).

11.14 (IH,s, 1soquinoline
-G,).

Reference examples 3 to 7. Synthesis of isoquinolinium halide compounds Using commercially available products or various cycloalkyl halides obtained in Reference Example 1 and isoquinoline as raw materials, reaction and post-treatment were carried out in the same manner as in Reference Example 2 to obtain the corresponding isoquinolinium halide. The compound was obtained. The results are shown in Table-1.

Margin reference example 8 below. Synthesis of TCNQ-Li salt 20.4g (0.1 mol) of TCNQ [manufactured by Wako Tsumugi Kogyo @] was added to 1.5 g of acetonitrile! 26.8 g (0.2 mol) of lithium iodide was dissolved in 200 g of acetonitrile.
A solution dissolved in mj was added dropwise and reacted under reflux for 1 hour. After the reaction, the mixture was cooled and the crystals were collected and dried to obtain 20.0 g of a purple powder (yield: 94.8%).

Example 1. Synthesis of 2-cyclohexylmethylisoquinolinium TCNQ single salt 4.6 g of 2-cyclohexylmethylisoquinolinium bromide obtained in Reference Example 2 was mixed with TC obtained in Reference Example 8.
Li salt of NQ: It was added to a solution of 1.17 g (15 mmol) in 150 mj of methanol and reacted under reflux for 2 hours. After the reaction, the reaction solution is cooled and the crystals are collected, washed and dried to give 2-cyclohexylmethylisoquinosonium TCN.
5.2 g of Q IF salt was obtained as a blue-purple powder (yield: 8
0.5%).

Elemental analysis value (CzaH24Ns) Theoretical value (!li) C near 8.11. H: 5.62
．． N: I8.27 Actual value (%) C near 7.82.
H: 5.8+, N: I6.37° DSC: Endothermic point 2'01°C 9 Exothermic decomposition point 248°C.

Examples 2-6. Synthesis of various isoquinolinium TCNQ single salts Using the isoquinolinium halide compounds obtained in Reference Examples 3 to 7 and the Li salt of TCNQ obtained in Reference Example 8, reaction and post-treatment were carried out in the same manner as in Example 1. The corresponding isoquinolinium TCNQ single salt was obtained. The results are shown in Table-2.

Practical Example 7, Synthesis of TCNQ'Jrf Formation 2.15 g (5 mmol) of the TCNQ single salt prepared in Example 1 and 1.02 g (5 mmol) of TCNQ were dissolved in 200 ml of acetonitrile under heating, and the solution was heated under reflux. The reaction was allowed to proceed for 2 hours. After the reaction, the crystals were collected by cooling and recrystallized from acetonitrile to obtain 2.70 g of black-purple prism crystals (
Yield 85.2%).

Elemental analysis value (04o11z8NJ theoretical value (sum C near 5.6'l, H: 4.45.N
:19.86 Actual value ($) C near 5.49. H:
4.5! l, N: 19.91° Specific resistance value: 140
Ω-cm.

DSC: Endothermic point 234°C: Exothermic decomposition point 273°C.

'I'GNQ'/Tl;NQ' ratio: 1.02 Examples 8-12. Synthesis of various TCNQ complexes Using the TCNQ single salts prepared in Examples 2 to 6, reactions and post-treatments were carried out in the same manner as in Example 7 to obtain corresponding TCNQ complexes. Display the results -
Shown in 3.

In addition, the complex composition ratio ('
r to NQ'/Tll:NQ'') is based on the literature (8, Rem
baum Ctal,.

J, 8m, CheLIl, Soc,, 93.25
:12 (+971)) by ultraviolet absorption spectrum measurement method. In addition, the endothermic point and exothermic decomposition point were determined by differential scanning calorimetry (OSC) measurement. Regarding the electrical property values, the complex was made into a pellet, and after preparing the sample according to the above conventional method, current and voltage measurements were carried out at 25°C (two-terminal method), and the specific resistance value ρ (Ω cm ) was calculated based on the surface calculation formula. I asked for it.

(Effects of the Invention) As described above, the present invention is characterized in that an N-substituted quinolinium cation, which has not been used in TCNQ complexes, is used as a donor. This invention has a remarkable effect in that it can provide a new TCNQ complex from which electrochemical or optical results can be expected, and it is a great invention that is dedicated to this industry.

Claims (1)

[Claims] Represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. N-substituted isoquinolinium cation and 7,7,8,8-tetracyanoquinodimethane anion radical (TCNQ) and neutral TCNQ (TCNQ°)
A TCNQ complex consisting of and.