JPS6263571A - Novel tcnq complex - Google Patents

Abstract

NEW MATERIAL:A TCNQ complex (D<+>.TCNQ<->.TCNQ deg.) consisting of a cation (D<+>) of N-aralkyl-substituted nitrogen-containing heterocyclic compound selected from the group consisting of compounds expressed by formula I-formula XV. USE:An electroconductive material usable in an organic semiconductor field such as highly functional electroconductive molecular membrane, non-linear optical material, design of highly ordered molecular aggregate having electric function and solid electrolyte for electrolytic condensers and batteries or cells, etc. PREPARATION:For example, a cation iodide (D<+>I<->) of the corresponding nitrogen-containing heterocyclic compound is reacted with a neutral TCNQ at 3:4 molar ratio to obtain D<+>.TCNQ, which is then doped with a neutral TCNQ to obtain a TCNQ complex.

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 has a structure in which TCNQ itself stacks up on its own. It exhibits high conductivity due to its characteristics.

TCNQ complexes are lightweight, conductive anisotropic, meltable, film-forming, and easy to process and mold.

It has the advantage of being able to utilize the characteristic properties of organic compounds as metals, and is therefore useful for electronic functions such as high-performance conductive molecular films, nonlinear optical materials, and applications of these molecular devices and biological devices. It is a compound that is highly expected to be used in the design of highly ordered molecular aggregates, solid electrolyte rings for electrolytic capacitors and batteries, and various organic semiconductor fields.

Regarding TCNQ complexes, a large number of cationic TCNQ complexes of nitrogen-containing heterocyclic compounds have been synthesized so far, but TCNQ complexes are originally organic compounds, and the structure can be changed little by little by changing substituents and constituent elements. By changing the properties, it is possible to optimize the various properties required as a conductor depending on the purpose, so we are developing new TCNQ complexes that can meet these various needs. development is desired.

[Objective of the Invention] The present invention was made in view of the above-mentioned current situation, and an object thereof is to provide a novel TCNQ complex that is an organic conductive compound and can be expected to have various electrochemical or photochemical results. shall be.

[Structure of the invention]

The present invention provides a cation (
D) and? , 7,8.8-tetracyanoquinodimethane anion radical (TCNQ7) and neutral TCNQ
(TCNQ”) and TCNQ complex (D”) as a constituent component
・TCN Q?・TCN Qo) invention.

The novel TCNQ complex of the present invention is a nitrogen-containing heterocyclic compound cation iodide D by utilizing the reducing property of the iodide ion I-.
``A method of reacting I- with neutral TCNQ at a molar ratio of 3:4, or a method of reacting /\logenide of the same cation D with TCNQ.
It can be easily synthesized by a method known per se, such as a method of reacting with a Li salt to obtain D"TCNQ" and doping this with neutral TCNQ.

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 1 For example, the specific resistance value can be determined by molding the sample powder into a pellet, measuring the current and voltage using the two-terminal method, and calculating the resistance value R using the following equation. ρ=R-A/cross, where ρ is the specific resistance value (Ω
・cm), R is resistance (Ω), A is electrode contact area (c
m") is the thickness of the sample, and the thermal properties can be measured by thermal analysis such as differential scanning calorimetry (DSC) measurements.

The novel TCNQ complex of the present invention has excellent conductivity, processability, and moldability, especially as a Chinese-German or mixed product, so it can be used for high-performance conductive molecular films, nonlinear optical materials, molecular devices thereof, and biological devices. It is expected that it can be effectively used in various organic semiconductor fields, such as in the design of highly ordered molecular assemblies with electronic functions, such as applications, or as solid electrolytes for electrolytic capacitors and batteries.

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

〔Example〕

Reference Example: Synthesis of N-7 ralkyl quaternary ammonium iodide (nitrogen-containing heterocyclic compound cation iodide) Mix moles of an organic base and aterkyl iodide without a solvent or in an appropriate organic solvent if necessary, Boiling point of solvent ~
The reaction was carried out at 120°C for 0.5 to 10 hours. After cooling, treat the reaction solution and transfer it to #book≠###). J Yuhi C or soot voice blue crystal rekiya prefecture L(.

r ira hf: N -'/'Larukiru No. e) r:
*1.

1-! ,,Self-example Synthesis of TCNQ complex 7 3.06g of TCNQ in 150rrLl of settonitrile
(15zIIlol) was dissolved by heating, and N-aralkyl quaternary ammonium iodide (15zIIlol) obtained in the reference example was added to this solution.
An acetonitrile solution in which il, 25 + o + ool) was dissolved was added dropwise, and the mixture was refluxed for 1 hour. After cooling, the precipitated crystals were separated into 7 pieces and recrystallized from acetonitrile to obtain TCN.
A Q complex was obtained.

The results for the TCNQja body obtained are shown in Table 2 (a
) to (C).

In the table, the complex composition ratio (TCNQ'pCNQ') of neutral TCNQ (indicated as TCNQ') and anion radical TCNQ (indicated as TCNQ'') is based on the literature (A, Re+sba
um etc.

J, Am, Chew, Soc,, 93.2j3
2 (1971)) using an ultraviolet absorption spectrum measurement method. In addition, the endothermic point and exothermic decomposition point were determined by differential scanning calorimetry (DSC) measurement. Regarding the electrical property values, the complex was made into a pellet, and after preparing the sample according to the conventional method, current and voltage measurements (two-terminal method) were performed at 25°C, and the specific resistance value ρ (Ω cm) was calculated based on the above calculation formula. I asked for it.

〔Effect of the invention〕

As described above-1-, the present invention uses the N-aralkyl-substituted nitrogen-containing heterocyclic compound cations shown in (1) to (15) above, which have not been used in TCNQ complexes, as donors. This invention has the following characteristics, and has a remarkable effect in that it can be provided on a new TCNQCN that can be expected to produce various electrochemical or photochemical results that have not been seen before.

Claims (1)

[Scope of Claims] A cation (D^+) of an N-aralkyl-substituted nitrogen-containing heterocyclic compound selected from the group consisting of (1) to (15) below, and 7,7,8,8-tetracyanoquino Dimethane anion radical (TCNQ^■) and neutral TCNQ (TCNQ
TCNQ complex (D^+・TC
NQ^■・TCNQ^■). (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ▲ Numerical formulas, chemical formulas, tables, etc. Yes ▼ (5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (6) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (7) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (8) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (9) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (10) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (11) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (12) ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (13)▲ There are mathematical formulas, chemical formulas, tables, etc.▼(14)▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (15) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼