JPH0678311B2 - 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 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 use in the design of highly ordered molecular assemblies having electronic functions such as application to these molecular devices and biological devices, or in various organic semiconductor fields such as solid capacitors for electrolytic capacitors and batteries. It 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 current situation as described above, 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.

[Structure of Invention]

The present invention has the formula (However, R represents an alkyl group having 1 to 8 carbon atoms) and 7,7,8,8-tetracyanoquinodimethane anion radical and an N-alkyl-4-phenylpyridinium cation And a TCNQ complex having neutral TCNQ (TCNQ °) as a constituent.

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

(In the formula, n represents an arbitrary number of 0.5 ≦ n ≦ 2.) In the TCNQ complex of the present invention, the formula of the donor part The alkyl group R of the N-alkyl-4-phenylpyridinium cation represented by is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
It represents an alkyl group having 1 to 8 carbon atoms such as a heptyl group and an octyl group, which may be linear or branched.

INDUSTRIAL APPLICABILITY The TCNQ complex of the present invention utilizes the reducibility of iodo ion I ⁻ to produce N-alkyl-4-phenylpyridinium cationic iodide And neutral TCNQ at a molar ratio of 3: 4, or by reacting the same cation halide and TCNQ Li salt. And can be easily synthesized by a method known per se, such as a method of doping this 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 properties 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. Therefore, it can be used as a highly functional conductive molecular film, a non-linear optical material, a molecular device or a biological device thereof. It can be expected that it can be effectively used in various organic semiconductor fields such as the design of highly ordered molecular assemblies having electronic functions such as application to, or as a solid electrolyte of electrolytic capacitors and batteries.

Examples will be shown below, but the present invention is not limited to these examples.

〔Example〕

Example 1. (1) Synthesis of N-n-butyl-4-phenylpyridinium iodide 4.7 g (0.03 mol) of 4-phenylpyridine and 5.6 g of n-butyl iodide were reacted by heating at 90 to 110 ° C for 15 minutes. The precipitated crystal was recrystallized from acetone-ethanol to obtain 9.2 g of a yellow powdery crystal of Nn-butyl-4-phenylpyridinium iodide. (Yield 90.4%) mp163-164 ℃ Elemental analysis value: C ₁₅ H ₁₈ NI Calculated value: C% 53.11, H% 5.35, N% 4.13 Actual value: C% 52.97, H% 5.42, N% 4.17 ¹ HNMR δppm _{(CDCI 3) 0.97 (3H,} t, J = 6Hz, N- (CH 2) 3 C H 3), 1.17~2.30 (4H, m, N-CH 2 C H 2 C H 2 CH 3), 4.89 ( 2H, t, J = 9Hz, N-C H 2 -) 7.40~7.60 (5H, m, aromatic), 8.25 (2H, d, J = 6Hz, pyridine-C 3, C 5), 9.13 (2H, d , J = 6Hz, pyridine-C 2, C 6) (2) the TCNQ3.06g the synthesis of acetonitrile 150ml of TCNQ complex (15 mmol) was dissolved with heating, to which N-n-butyl-4-phenyl pyridinium iodide 3.82 100 ml of acetonitrile solution containing g
Was added dropwise, and the mixture was refluxed for 1 hour. The reaction solution was cooled, the precipitated crystals were taken, and recrystallized from acetonitrile.3.
7 g of black-purple needle crystals were obtained. (Yield 79.4%) Elemental analysis value: C ₃₉ H ₂₆ N ₉ Calculated value: C% 75.47, H% 4.22, N% 20.31 Actual value: C% 75.25, H% 4.38, N% 20.37 Specific resistance value: 8Ω ・cm DSC measurement: endothermic point 247 ℃; exothermic decomposition point 279 ℃ The neutral TCNQ (denoted as TCNQ °) and the anion radical TCNQ Complex composition ratio with (A. Rembaum etc., J. Am. Chem. Soc., 93 , 2532 (19
71)) according to the ultraviolet absorption spectrum measurement method.
The differential scanning calorific value (DS
C) Obtained by measurement. Regarding the electrical characteristic values, the complex was made into pellets, and the sample was prepared according to the conventional method, and then the current-voltage measurement (two-terminal method) was performed at 25 ° C. to determine the specific resistance value ρ (Ωcm) based on the above calculation formula.

Examples 2 to 10 (1) Synthesis of N-alkyl-4-phenylpyridinium iodide Equimolar 4-phenylpyridine and various alkyl iodides were mixed in a solvent-free or suitable organic solvent, and 90-12
The reaction was carried out at 0 ° C. (under solvent reflux when using a solvent) for 0.5 to 10 hours. After cooling, the precipitated crystals were taken and recrystallized from acetone or acetone-ethanol to give various N-alkyl-4.
-Phenylpyridinium iodide was obtained. The results are shown in Tables 1 (a) and (b).

(2) Synthesis of TCNQ complex TCNQ (3.06 g, 15 mmol) was dissolved in 150 ml of acetonitrile under heating, and the various N-alkyl-4-phenylpyridinium iodides (11.25 mmol) obtained in (1) were dissolved in this acetonitrile solution. Was added dropwise, and the mixture was refluxed for 1 hour.
After cooling, the precipitated crystals are taken and recrystallized from acetonitrile.
A TCNQ complex was obtained. The results are shown in Tables 2 (a) and (b).

[Effects of the Invention] As described above, the present invention is an invention characterized by using an N-alkyl-4-phenylpyridinium cation, which has not been used in TCNQ complexes, as a donor, and is unprecedented. The present invention has a remarkable effect in that it can provide a novel TCNQ complex that can be expected to have various electrochemical or optical results, and is a great invention that contributes to the art.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location H01L 31/0344

Claims (1)

[Claims] 1. A formula (Wherein R represents an alkyl group having 1 to 8 carbon atoms) and an N-alkyl-4-phenylpyridinium cation and 7,7,8,8-tetracyanoquinodimethane anion radical And a TCNQ complex containing neutral TCNQ (TCNQ °) as a constituent component.