JPS6391386A - Novel tcnq complex - Google Patents

Abstract

NEW MATERIAL:The TCNQ complex consisting of a 4-phenyl-N-substituted- pyridinium cation of formula I [R<1> is group of formula II or III (R<2> and R<3> are H or 1-8C alkyl; l and m are 1-4); n is 1-4], 7,7,8,8- tetracyanoquinodimethane anion radical (TCNQ<->) and neutral TCNQ (TCNQ<0>) as constituent components. USE:An electrically conductive material. PREPARATION:For example, a halogenated 4-phenyl-N-substituted-pyridinium cation is made to react with Li salt of TCNQ and doping neutral TCNQ to the resultant compound of formula IV.

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 and forms extremely stable radical salts with cations. It exhibits high electrical conductivity due to its unique stacking structural feature.

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. It is a compound that is highly expected to be used in 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. Since the properties can be changed, 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 aims to provide a novel TCNQ complex which is an organic conductive compound and is expected to have various electrochemical or photochemical results. purpose.

[Structure of the invention]

The present invention is represented by the formula (where R2 and R3 are hydrogen or have 1 to 8 carbon atoms,
It represents an alkyl group, and l and m represent integers of 1 to 4. ),
n represents an integer of 1 to 4. ] and 4-phenyl-N-substituted pyridinium cation represented by 7,7,8.8-
Tetracyanoquinodimethane anion radical (TCNQ
? ) and neutral TCNQ (TCNQ).

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

(In the formula, k represents an arbitrary number between 0.5≦ and ≦2.0.) n represents an arbitrary integer from 1 to 4.

Also, R2 in the above ■ and ■. R3 is hydrogen, or a linear or terminally branched alkyl group having 1 to 8 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, or octyl group. It and m represent any integer from 1 to 4.

The TCNQ complex of the present invention can be prepared by methods known per se, for example, 4-
It can be easily synthesized by a method of doping neutral TCNQ by reacting a halide of a phenyl-N-substituted pyridinium cation with a Li salt of TCNQ. Examples of halides of 4-phenyl-N-substituted pyridinium cations include compound X-(C)12).

-R' (in the formula, X represents halogen, R1 and n are the same as above) can be easily obtained by reacting with 4-phenylpyridine in the presence of an appropriate solvent if necessary, It is sufficient to use what is obtained in this way. X-(coz). For the compound represented by -RI, a commercially available reagent may be used as it is, or if necessary, it may be appropriately synthesized according to a method described in a literature and used. That is, for example, when synthesizing the same compound 0 as above, J, Org, Ch
Em,.

34, 1122 (1969), J. Am, Che.
m, Sac, 70.3781 (1948), He
1v, Chirn, Acta, 32.2151
(1949).

This may be carried out according to the method described in British Patent No. 728,446, etc., and the compounds used, for example, are the same as those described above. ), U.S. Patent No. 2,860,146
No., Ann, 59B, 1.102,141. (1
955) Bulletin de la Socigt
g Ghimique de France.

[5] 12.827 (1945), Gazzetta
Chimica Italiana.

86, 178 (1956), J. Chem, Sa.
It is sufficient to carry out this according to the method described in, for example, 1953.618. In addition, the TCNQ complex of the present invention utilizes the reducing power of iodo ion to produce 4-phenyl-N-
It goes without saying that it can be similarly synthesized by a method in which substituted pyridinium cations are reacted at an iodide ratio of 3:4.

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/1°, where ρ is the upper resistance value (Ω・cm), R is the resistance (Ω), A is the electrode contact area (crn”), and j! is the sample thickness (co+). be.

Further, 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 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〕

Example 1゜(1) Synthesis of 1-(2-(1,3-dioxan-2-yl)ethyl]-4-phenylpyridinium bromide 4-phenylpyridine (manufactured by Aldrich) 7.8 g
(50 mmol) and 2-(2-bromoethyl)-1,3
- 9.8 g of dioxane (manufactured by Aldrich) at 70-8
The reaction was carried out at 0°C for 1 hour. After the reaction, acetone was poured into the reaction solution to crystallize the desired product, and the precipitated crystals were collected and dried to obtain 13.9 g of white crystalline powder (yield: 79.0%).

mp: 177-179°C Elemental analysis value ((, J2oBrNO,) Calculated value = C%58.30. H%5.76, N%4
．． 00 Actual value: 6%58.19. H%5.88.
N%4.13゜HNMR: δppm (CD e
ll s)m, benzene ring) , 8.39 (211,
d, J-7Hz, pyridine ring C3, C5 hydrogen), 9.
64 (2H, d, J-7Hz.

pyridine ring C2, C6 hydrogen).

(2) Synthesis of TCNQ-Li salt TCNQ [manufactured by Wako Pure Chemical Industries, Ltd.] 20.4g (0,
A solution of 26.8 g (0.2 mol) of lithium iodide dissolved in 200 g of acetonitrile was added dropwise to the solution under reflux.
Allowed time to react. After the reaction, the crystals were collected by cooling and dried to obtain 20.0 g of a purple powder (yield: 94.8%).
.

(3) Synthesis of TCNQ single salt 2.11 g (10 mmol) of the Li salt of TCNQ obtained in (2) was dissolved in 90 Inl of methanol under heating, and the mixture was dissolved in (
1-r2-(13-dioxan-2-yl) obtained in 1)
ethyl]-4-phenylpyridinium bromide 3.5
A solution of g (10 mmol) dissolved in 25 mj of methanol was added dropwise, and the mixture was reacted under reflux for 2 hours. After the reaction, the crystals are collected by cooling, washed and dried to give 1-[2-(1,
1.62 g of 3-dioxan-2-yl)ethyl]-4-phenylpyridinium TCNQ monosalt was obtained as a purple powder (yield: 34.1%).

Elemental analysis value (C2Jz<N502) Calculated value = C%73.40. H%5.10. N%14.
76 Actual value = C% 73.13. H%5.33. N%1
4.79°DSC: Endothermic point 148°C; Exothermic decomposition point 245
℃.

(4) Synthesis of TCNQ complex 1.42 g (3 mmol) of the TCNQ single salt obtained in (3) and 61 g (3 mmol) of TCNQ O were dissolved in 90 mZ of acetonitrile under heating, and the reaction was carried out under reflux for 2 hours. went.

After the reaction, the crystals were collected by cooling and recrystallized from acetonitrile to obtain 1.50 g of black-purple prism crystals (yield:
74.0%).

Elemental analysis value (G41) 128N90□) Calculated value = C%7
2.55. H%4.16. N%18.57 Actual value = C
%72.19. H%4.33. N% 18.81° Specific resistance value: 22Ω・C111.

DSC: Endothermic point 242°C: Exothermic decomposition point 268°C.

TCNQ'/TCNQ'' ratio: 1.01°, neutral TC
NQ (denoted as TCNQ') and anion radical TCNQ
(expressed as “TCNQ”) and the complex composition ratio (T(:NQ’/
TCNQ') is based on the literature (A, Rembaun+ et a
l.

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 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・c-re) was determined based on the above calculation formula. I asked for

〔Effect of the invention〕

As described above, the present invention is characterized in that it uses a 4-phenyl-N-substituted viridinium cation, which has not been used in TCNQ complexes, as a donor, and it has various electron This invention has remarkable effects in that it can provide a novel TCNQ complex that can be expected to produce chemical or optical results, and is a great invention that contributes to this industry.

Patent Applicant: Wako Pure Chemical Industries, Ltd. Procedural Amendment February 27, 1988 1. Indication of the Case 1988 Patent Application No. 238589 2. Name of the Invention New TCNQ Complex 3. Relationship with the Amendment Case Patent applicant postal code 541 Contact information 7): L03-270-85714, Date of amendment order 5, Detailed description of the invention in the specification to be amended.

6. Contents of amendment (1) “C Chia 3.13 stated on page 10, line 10 of the specification
Correct J to "Cchi 73.17J.

that's all

Claims (1)

[Claims] Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^1 indicates ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, , R^2, R^3 represent hydrogen or an alkyl group having 1 to 8 carbon atoms, and l and m represent integers of 1 to 4.)
n represents an integer of 1 to 4. ] and 4-phenyl-N-substituted pyridinium cation represented by 7,7,8,8-
Tetracyanoquinodimethane anion radical (TCNQ
^-) and neutral TCNQ (TCNQ^+) as constituent components.