JPS63159368A - Novel tcnq complex - Google Patents

Abstract

NEW MATERIAL:A TCNQ complex containing a 1-substituted-4-[2-phenyl(or substituted)ethenylpyridinium cation expressed by formula I [R<1> is H, lower alkyl, lower alkoxy, nitro, cyano, OH, CF3 or F; R<2> is 1-8C alkyl, -(CH2)mOCH3 (m is 2-5)], 7,7,8,8-tetracyanoquinodimethane anionic radical and neutral TCNQ as constituent components. EXAMPLE:1-n-Butyl-4-(2-phenylethenyl)pyridinium TCNQ complex. USE:Useful in the field of application to highly functional electrically conductive films, nonlinear optical materials, design of highly ordered molecular aggregates, organic semiconductors, e.g. solid electrolytes in electrolytic condensers, cells or batteries, etc. PREPARATION:For example, a compound expressed by formula II is reacted with neutral TCNQ at 3:4 molar ratio to afford the aimed compound expressed by formula I.

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 I:1 conductivity due to its unique structural feature of stacking.

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, the application of high-performance conductive molecule 11Q, nonlinear optical materials, antistatic agents, molecular devices, and biological devices,
It is a compound that is highly expected to be used in various organic semiconductor fields, such as in the design of highly ordered molecular aggregates with electronic functions, and in solid electrolytes for electrolytic capacitors and batteries.

Regarding TCNQ complexes, a large number of cationic TCNQ complexes of nitrogen-containing heterospecies 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. Since the properties can be changed, it is possible to optimize the various properties required as a conductor. Development of complexes is desired.

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

[Structure of the invention]

The present invention is based on the formula [where R1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a cyano group, a hydroxyl group, a trifluoromethyl group, or a fluorine atom, and R2 represents an alkyl group having 1 to 8 carbon atoms or =(GH2)1. , l0CI+3 groups (however,
m=an integer from 2 to 5). l-substitution represented by
Consists of 4-[2-phenyl (or substituted phenyl) nibnyl J pyridinium cation, 7,7゜8.8-tetracyanoquinodimethane anion radical (TCNQ') and neutral TCNQ (TCNQ'') TCNQ
This is an invention of a complex.

The TCNQ complex of the present invention is represented by, for example, F.

(In the formula, X represents an arbitrary number such as 0.5≦X≦2.0.) In the TCNQ complex of the present invention, R ' represents a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a lower alkoxy group such as a methoxy group or an ethoxy group, a nitro group, a cyanoel group, a hydroxyl group, a trifluoromethyl group, or a fluorine atom; R2 has 1 to 1 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group, an octyl group, etc.
8, a linear or terminally branched alkyl group, such as a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxyamyl group, etc., of the formula -(C112),
It represents a methoxyalkyl group represented by 10C113 (where m=an integer of 2 to 5).

The TCNQ complex of the present invention can be produced by a method known per se, for example, by utilizing the reducing property of iodo ion 1-, 1-substituted 1-4-[2-
phenyl (or substituted phenyl)nibnyl] and neutral TCN
It can be easily obtained by a method of reacting Q at a molar ratio of 3:4. 1-Substituted-4-[2-phenyl (or substituted phenyl)ethynyl]pyridinium iodide is described, for example, in J, Org.

Ghem, 28.387 (1963), J.Org.
,(t+em,,21.1039(1956),J,(
:hem, Soc,, 1960.1516, J, Che
m,Soc,.

1934, 276, etc., by reacting γ-picoline with benzaldehyde or substituted benzaldehyde in acetic anhydride to produce 4-[2-phenyl (or substituted phenyl)nibnyl-1-pyridine, as appropriate. Since it can be easily obtained by reacting with an alkyl iotide or a methoxyalkyl iotide in the presence of a suitable solvent, it is sufficient to use the product obtained in this way. Methoxyalkyl iodide is, for example, 1.1. Am, Chem, Soc,, 72
．． Methoxyalkyl chloride is synthesized from alkyl chloride and metal methylate according to the method described in I:l34 (1950) etc., and then it is easily obtained by heating and reacting it with alkali iodide in a suitable solvent in a conventional manner. You can use the one obtained in this way.

Moreover, the TCNQ complex of the present invention has 1-substituted-4-[2-
phenyl (or substituted phenyl) nibnyl] 1j? It goes without saying that it can be synthesized in the same manner by a method in which neutral TCNQ is stiffly topped.

The synthesized TCNQ complex of the present invention can be identified by the color characteristic of charge transfer complexes and the appearance of a charge transfer absorption band, and the complex composition ratio can be determined from elemental analysis and measurement of ultraviolet absorption spectra. Electrical properties, such as specific resistance values, can be determined by applying the sample powder to a pellet, measuring the current and voltage using the two-wire f-method, calculating the resistance value R, and using the following equation. p=R・A/n0 However, ρ is the specific resistance i (
Ω・cm), R is the resistance (Ω), A is the electrode contact area (c
rn'), 1 is J''1cm) of the sample.Thermal properties can also be measured by thermal analysis such as differential scanning calorimetry'+t (D S C) measurement.

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

Although Examples and Reference Examples are shown below, the present invention is not intended to be in any way limited by these Examples or Reference Examples.

(Example) Reference example 1. Synthesis of 4-(2-phenylethynyl)pyridine 9.3 g (0.1 mol) of γ-picoline, 6 g (0.1 mol) of penzartecht IO, and 10.2 g of acetic anhydride.
(0.1 mol) were mixed and reacted under reflux for 10 hours.

Next, 200 ml of water was added and concentrated under reduced pressure. After cooling, the precipitated crystals were collected, washed with water and alcohol, and dried to obtain a crude product of 16.5
It was gwo It. This was recrystallized from ethanol and 4-(2
-Phenylethynyl)pyridine as pale yellowish brown flaky crystals6.
5 g was obtained (yield 35.9%).

mP127-128°C.

Reference Examples 2 to 10 Nine types of 4-(2-substituted phenylethynyl)pyridine were obtained in the same manner as in Reference Example 1 using nine types of substituted benzaldehydes. The results are shown in Table 1.

Table 1 □□Yo Example 1. Synthesis of 1-n-butyl-4-(2-phenylethynyl)pyridinium TCNQZff compound (Ill-n
-Butyl-4-(2-phenylethynyl) Synthesis of pyricinium aodite In Reference Example 1, 3.6 g (20 mmol) of IH+4-(2-phenylethynyl)pyridine was iodized in ethanol.
A continuous flow reaction was carried out with 3.7 g of butyl for 1.5 hours. The reaction solution was then concentrated (under reduced pressure)', the residue was crystallized from acetone and ethanol, the precipitated crystals were scraped off, and recrystallized from acetone-ethanol to give 1-n-butyl-4-(2-phenylethynyl)pyricinium salt. rOdide yellow powder product 4
．． 0 g was obtained (yield 55.1%).

mp　1841-185℃.

'HN M R699m (CDO1+ DMSO-d
,,):0.9B(311,L,J-611y,-(:
1hclI2clI□e11. ), 1.2:1-2.
32 (411, m, -(:1hCIhCIhC1h)
, 4.6:l (211, L , J = 711z
, 5 N'(:1hClbC1hCIL+) near, 2
2 to 8.07 (711, m, benzene ring hydrogen and -c!
! -cIm), 8.20 (211,d, J-711z
, pyridine C3, C, hydrogen), 3.97 (211,
d, J-711z, pyridine feed C2, Cr, hydrogen).

Elemental analysis value (CI78201 N) Theoretical value (%) C: 55.90. H: 5.52.
N: :1.8:1 Real 4! Value (!t:) C: 5
5.72. H: 5.61. N: :], 86゜i
2) Synthesis of TCNQ complex 3.06 g of 7,7,8.8-detracyanoquinosimethane
(15 mmol) was dissolved in 150 ml of acetonitrile under heating, and 1-n-butyl-4-(
A solution of 2-phenylethynylacetonitrile was added dropwise and the mixture was refluxed for 1 hour.

The reaction solution was cooled, the precipitated crystals were collected, and recrystallized from acetonitrile to obtain black-purple prism crystals of 1-n-butyl-4-(2-phenylethynyl)pyridium TCNQ complex 4.1
g (yield 84.6%).

Elemental analysis value (CJIH28N9) Theoretical value (1) C: 76, 14, H: 4.36,
N: 19.49 actual value (sum C: 76,02, H:
4.52, N: 19.46.

Specific resistance value: 27Ω・CIll.

DSC: Endothermic point 253°C; exothermic decomposition point 270°C.

TCNQnTCNQ' ratio = 1.00.

Examples 2 to 20. Synthesis of 1-substituted-4-(2-substituted phenylethynyl)pyridinium TCNQ complex (1) Synthesis of 1-substituted-4-(2-substituted phenylethynyl)pyridinium iodide Example 1 to Nineteen types of 1-substituted -4-(2-
Substituted phenylethynyl)pyridinium iodide 4
17. The results are shown in Tables 2 (1) to (4).

f2) Synthesis of TCNQ complex + Using 19 kinds of 1-substituted-4-(2-substituted phenylethynyl)pyridinium iodides obtained in step 11, 19 kinds of TCNQ complexes were synthesized by IH+ in the same manner as in (2) of Example 1.
Ta. The results are shown in Tables 3 (1) to (3).

In addition, the complex composition ratio ('
"(:NQ'/Tf;Nil") is the document (A, Remb
aum et al.

J, 8m, Chem, Soc, Seal, 25:1
2 (1971)) by ultraviolet absorption spectrum measurement method 1. Also, regarding the endothermic point and exothermic decomposition point, use differential scanning calorimetry (DSC)? It was determined using the 1llI constant. Regarding the electrical characteristic values, the complex was used as a pellet, and the sample was prepared according to the conventional method. Current and voltage measurements (two-terminal method) were carried out at
) was sought.

(Effects of the Invention) As described below, the present invention provides 1-substituted-4-[2-phenyl(
The present invention is characterized in that a substituted phenyl)ethynyl 1-pyridinium cation is used as a donor, and it can provide a novel TCNQ complex that can be expected to produce various electrochemical or optical results that have not been seen before. It has a remarkable effect on the industry, and it is a great invention.

Claims (1)

[Claims] Formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, R^1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, a cyano group, a hydroxyl group, a trifluoromethyl group, or a fluorine atom , and R^2 represents an alkyl group having 1 to 8 carbon atoms or a -(CH_2)_mOCH_3 group (where m is an integer of 2 to 5). ] 1-substituted-4-[2-phenyl (or substituted phenyl) ethenyl]
TC whose constituent components are pyridinium cation, 7,7,8,8-tetracyanoquinodimethane anion radical (TCNQ^-) and neutral TCNQ (TCNQ^+)
NQ complex.