JPS6344563A - Tcnq complex - Google Patents

Abstract

NEW MATERIAL:A TCNQ complex containing N-fluoroalkyl-4-phenylpyridinium cation of formula I [R<1> is F, CF3, CH(CH3)2, CF(CF3)2 or (CF2)nCF3 (n is 1-3); m is 2-7], 7,7,8,8-tetracyanoquinodimethane anion radical (TCNQ) and a neutral TCNQ as constituent components. EXAMPLE:N-(4,4,4-trifluorobutyl)-4-phenylpyridinium TCNQ complex. USE:An electrically conductive material, etc., applicable to high-performance electrically conductive molecular film, non-linear optical material, antistatic agent, molecular element and biological element. PREPARATION:The compound of formula I can be produced e.g. by reacting an N-fluoroalkyl-4-phenylpyridinium iodide of formula II with a neutral TCNQ at a molar ratio of 3:4.

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]

It is a charge transfer type complex compound, and its constituent component TCN
Q accepts electrons and forms extremely stable radical salts with cations, and TCNQ itself exhibits high conductivity due to its unique structural feature of stacking up.

The TCNQ complex combines the characteristic properties of organic compounds, such as light weight, anisotropy of conductivity, meltability, film-forming properties, and ease of processing and molding, with the advantages of metals. Therefore, it is useful for applications in high-performance conductive molecular films, nonlinear optical materials, antistatic agents, molecular devices, biological devices, the design of high-chip molecular aggregates with electronic functions, or electrolytic capacitors and For various organic semiconductor fields such as solid electrolytes for batteries,
This is a compound that is highly anticipated for its use.

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 can be changed by changing the substituents and constituent elements. This makes it possible to optimize the various properties 71 required as a conductor depending on the purpose, and it is therefore desirable to develop new TCNQ complexes 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 TCNQjR compound which is an organic conductive compound and is expected to have various electrochemical or photochemical results.

[Structure of the invention]

The present invention represents the formula %Formula %:3) or 1cF2)nC+':+ (where n represents an integer of 1 to 3), and m represents an integer of 2 to 7. ] N-fluoroalkyl-4-phenylpyridinium cation and 7,7,8.8-tetracyanoquinodimethane anion radical (TCNQ and neutral TCNQ
(TCNQ') as a constituent component.

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

(In the formula, X represents an arbitrary number such as 0.5≦X≦2.0.) In the TCNQ complex of the present invention, the donor part has the formula 0 formula % -(CF2). (:F3 (where n represents an integer of 1 to 3), and m of -(CH2), -R'' represents an integer of 2 to 7.

The TCNQ complex of the present invention can be easily obtained by a method known per se, for example, by utilizing the reducing property of iodo ion l- and reacting it with N-fluoroalkyl-4-phenylpyridinium ion at a molar ratio of 3:4. Can be done. The N-fluoroalkyl-4-phenylpyridinium iodide used in the present invention is, for example, J, Am, Chem.
, Soc, 77, :+637 (1955); J
, Org, Chem, 15.425 (1949);
J, Org.

Chem, 21.748 (+956); Journal of the Society of Organic Synthetic Chemistry.

34, (10) 722 (+976) etc. can be easily obtained by reacting it with 4-phenylpyridine in the presence of an appropriate solvent if necessary. , it is sufficient to use the one obtained in this way.

It goes without saying that the TCNQ complex of the present invention can be similarly synthesized by a method of doping TCNQ by reacting a halide of N-fluoroalkyl-4-phenylpyridinium thione with a Li salt of 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, 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/u. However, p is the specific resistance value (Ω・
cm), R is resistance (Ω), A is electrode contact area (cm')
, ffi is the sample thickness (cm). Further, the thermal properties can be measured by thermal analysis such as differential scanning calorimetry (D, SC) measurement.

The novel TCNQ complex of the present invention has excellent conductivity, processability, and moldability, especially when used alone or as a mixture, 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 aggregates with electronic functions, such as in applications, and as solid electrolytes for electrolytic capacitors and batteries.

Examples and reference examples are shown below, but the present invention is not subject to equivalent restrictions by these examples and reference examples.

〔Example〕

Reference example 1. 1,1.1-Synthesis of trifluoro-4-iodobutane +11 Synthesis of ethyl 4,4.4-trifluorobutyrate 4
．． 4. 10 g (0,017 mol) of ethyl 4-1-lifluorocrotonate (Aldrich '3J) was catalytically reduced at room temperature and pressure under a platinum oxide catalyst in ether, and the reaction solution was
After filtration, concentrate the liquid and distill the residue to obtain bp126-12
9°C fraction (ethyl 4,4,4-trifluorobutyrate) 7
．． Obtained 8 g as a colorless oil (yield 77%, GCC
content 981%), (literature value) bp: 126-129°C [
E,T.

McBec ct al,, J, Am, Chem, S
oc,,72,5071(1950)]+2) 4,
4. 4 obtained in synthesis (1) of 4-trifluorobutanol
, 4.4-) The reaction was carried out under reflux for 6 hours with 7.5 g of ethyl refluorobutyrate. After the reaction, add water to remove excess LiAIH.
, and distilled the residue obtained by concentrating the ether layer to obtain 3.8 g of a bp 124-125°C fraction (4,4,4-trifluorobutanol) as a colorless oil (yield 67%, Gc including debt 98.5%), (literature value) b
p: I24-125°C [tl, M, Walbors
ky ct at,.

J, 8m, chem, soc, , 77.3637
(1955)].

(311,4,4-Trifluorobutanol obtained in synthesis (2) of 1,1,1-trifluoro-4-iodobutanol 3
．． 6g (0,028mol) of potassium iodide 18.6
After reacting with g and 13.5 g of phosphoric acid under reflux for 13 hours, the reaction solution was poured into ice water and extracted with ether. The separated ether layer was dried over anhydrous magnesium sulfate, concentrated, and the residue was distilled to bp! 25-127℃ fraction (+,
1.1-trifluoro-4-iodobutane) 3.3
g was obtained as a colorless oil (yield 50%, GC content 9
8.9%).・ (Literature value) b p: 126-127°C [Il, M,
WalborskyeL al,,-J,8m,c
hem, soc,, 77.3637 (1'955)
].

'HNMR: δppm (CD 113) 1.83-2.
50(2H,o, CF3C82G+12(:H2T)
, 3.13~3.3'7 (4H,m,CF3CHi
C112CH1[).

Example 1゜+11 N-(4,4,4-trifluorobutyl)-
Synthesis of 4-phenylpyridinium iodide 4-phenylpyridine [manufactured by Wako Pure Chemical Industries, Ltd.] 980 mg (6,3
mmol) and 1.5 g of 1,1.1-)lifluoro-4-iodobutane obtained in Reference Example 1 at 110 to 130°C.
Allowed time to react. Ethyl acetate is poured into the reaction solution to crystallize the target product, and the precipitated crystals are collected and dried to obtain a yellowish brown powder product 1.
44 g was obtained (yield 58.0%).

mp: 177-178°C.

Elemental analysis Il(';+sH+5hlN) Calculated value = C%
44.68. H%3.75. N% 3.47 Actual value = C% 44.42. H%3.88. N%3.59
゜'HNMR: δpprn (CD C23), Φ (2H, t, J-7Hx, , N-C1j, CH, -)
, 7.50 to 7.93 (511° self, benzene ring hydrogen), 8.27 (2) 1. d, J=7Hz, hydrogen of pyridine ring C,, C5), 9.60 (2H, d, J
-7Hz.

pyridine ring C,, hydrogen of C6).

(2) N-(4,4,4-trifluorobutyl)-
Synthesis of 4-phenylpyridinium TCN Qi form 0.9 g (4.4 mmol) of TCNQ [manufactured by Wako Pure Chemical Industries, Ltd.] was dissolved in 50 rnl of acetonitrile, and the N-(4,4 mmol) obtained in (1) was dissolved therein by heating. ,4-)lifluorobutyl)
An acetonitrile solution in which 1.3 g of -4-phenylpyridinium iodide was dissolved was added dropwise, and the mixture was reacted under reflux for 1 hour. After the reaction, the reaction solution was cooled, the precipitated crystals were collected, and recrystallized from acetonitrile.1. Black-purple needle crystals of Ig were obtained (yield 74.0%).

Elemental analysis value ((:3sl12shNs) Calculated value: 0%6
8.42. H%3.39. H%18.41 Actual value: 0
%68.09. H%3.42. N% + 8.66° specific resistance (t'f: 8Ω-cm.

DSC: Endothermic point 242°C; exothermic decomposition point 277°C.

TCNQ'/TCNQ'' ratio = 1.01゜Also, neutral TC
NQ (expressed as “TCNQ”) and anion radical TCNQ
(expressed as TCNQ') and the complex composition ratio (TCNQ'/T
(:NQ”) refers to the literature (A, Rembaum et al.
,.

J, Am, Chew, Soc,, 93.253
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 characteristic values, the complex was made into a pellet, and after the sample was prepared according to the conventional method, current and voltage measurements (two-terminal method) were performed at 25°C, and the specific resistance value ρ (Ω・cva) was determined based on the above calculation formula. Ta.

〔Effect of the invention〕

As mentioned above, the present invention is characterized in that N-fluoroalkyl-4-phenylpyridinium cation, which has not been used in TCNQ complexes so far, is used as a donor, and it is characterized by the use of various electrochemical It has a remarkable effect in that it can provide a new TCNQ complex that can be expected to produce desired and optical results, and in particular, it has excellent heat resistance due to the introduction of fluorine into a part of the donor. It is a great invention that can be expected to have effects and contribute to this industry.

Claims (1)

[Claims] Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^f is -F, -CF_3, -CH (CF_3
)_2, -CF(CF_3)_2 or -(CF_2)_
nCF_3 (where n represents an integer of 1 to 3), and m represents an integer of 2 to 7. ] N-fluoroalkyl-4-phenylpyridinium cation represented by 7
, 7,8,8-tetracyanoquinodimethane anion radical (TCNQ^-) and neutral TCNQ (TCNQ^4
) as a constituent component.