JPH0158183B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel tetracyanoquinodimethane complexes. For details, see 1, 4, 8, 11.
-Relates to a tetracyanoquinodimethane complex containing tetraazacyclodecane. In recent years, it has been discovered that complexes of tetracyanoquinodimethane with alkali metal salts and electron-donating compounds have high electrical conductivity as organic compounds, and research on their physical properties and research has been actively conducted. On the other hand, it is known that cyclic polyethers, so-called crown ethers, form complexes with various metal salts. The present inventors also discovered that by reacting a metal salt of tetracyanoquinodimethane with a crown ether, a novel tetracyanoquinodimethane complex having higher electrolyte and conductivity with respect to organic solvents is formed. Already proposed. (Japanese Patent Application No. 55-144135, etc.) The present inventors conducted further studies and found that 1,4, which is a cyclic polyamine in place of crown ether,
When 8,11-tetraazacyclotetradecane was used, it was discovered that it forms complexes with a wider variety of metal ions and also forms stable complexes with polyvalent cations, thereby completing the present invention. I reached it. That is, the gist of the present invention is the general formula (Cyc) _l・mM ⁿ⁺ (TCNQ ^- ) _p・(TCNQ) _q・
Cl ^- _r・(sH ₂ O) _t ... () (In the formula, Cyc represents 1,4,8,11-tetraazacyclotetradecane; M is hydrogen or nickel, copper, zinc, cobalt, manganese, paldium , represents a transition metal atom selected from rhodium and lanthanum; TCNQ represents tetracyanoquinodimethane; l represents 1 or 2; m represents 1 to 4 when M is hydrogen; M is a transition metal atom When 1
n represents 1 to 3; p and q represent 0 to 4; r represents 0 to 2; s represents 1 or 2; t represents 0 or 1; ) exists in the tetracyanoquinodimethane complex represented by To explain the present invention below, the tetracyanoquinodimethane complex of the present invention is represented by the general formula (). When considering conductivity, the above general formula ()
Preferably, M is hydrogen, cobalt, lanthanum, manganese, or palladium. The tetracyanoquinodimethane complex of the present invention can be easily produced, for example, according to the following formula. M ⁿ⁺ Cl ^- _o +Cyc→(Cyc)M ⁿ⁺ Cl ^- _o (Cyc)M ⁿ⁺ Cl ^- _o +Li ⁺ TCNQ ^- →(Cyc)M ⁿ⁺ (TCNQ−)Cl ^- _o-1 Cyc+4HI→(Cyc)4H ⁺ I ^- ₄ (Cyc)4H ⁺ I ^- ₄ +4Li ⁺ TCNQ ^- → (Cyc)4H ⁺ (TCNQ−) ₄ (In the above formula, Cyc, M, TCNQ, and n have the same meanings as above.) That is, 1.4, 8 , 11-tetraazacyclotetradecane and a metal salt or hydrogen iodide are reacted in a solvent to form a complex, and then the tetracyanoquinodimethane of the present invention can be easily prepared by reacting with a lithium salt of tetracyanoquinodimethane. Quinodimethane complexes can be produced. Examples of the solvent used in the above reactions include alcohols such as methanol and ethanol, aprotic polar solvents such as acetonitrile and dimethylformamide, and water. The reaction is usually carried out at room temperature, and if necessary, by heating to the boiling point of the solvent. After the reaction, the precipitate precipitated is separated, washed with a reaction solvent or an organic solvent such as ether or acetone, and then dried to obtain the tetracyanoquinodimethane complex of the present invention. The tetracyanoquinodimethane complex of the present invention thus obtained has a cyclic polyamine and therefore has higher solubility in organic solvents than metal salts of tetracyanoquinodimethane. In addition, since complexes can be formed with many metal salts, by selecting the type of metal salt, complexes with various conductivities can be easily provided, allowing for a wider range of applications as new conductive materials. There is expected. The present invention will be explained in more detail with reference to Examples below. Example 1 An ethanol solution of 1 to 3 times the mole of an inorganic salt was added to an ethanol solution of 1,4,8,11-tetraazacyclotetradecane, and the mixture was stirred at room temperature. The generated precipitate was separated and dried to obtain an inorganic salt complex. Among the obtained inorganic salt complexes, the nickel complex and the copper complex were dissolved in acetonitrile, and an equimolar ethanol solution of a lithium salt of tetracyanoquinodimethane was added dropwise to this solution. The generated precipitate was separated, washed with ethanol, and then dried to obtain a tetracyanoquinodimethane complex. In addition, other inorganic salt complexes were dissolved in water to form an aqueous solution, and a lithium salt aqueous solution of 1.1 times the mole of tetracyanoquinodimethane was added dropwise to this aqueous solution. The generated precipitate was separated, washed with water, and dried to obtain a tetracyanoquinodimethane complex. The results are shown in Table 1.

【table】

[Table] Figure 1 shows the electronic spectra of complexes No. 1 to 3 in Table 1.
It was as shown in. Further, the specific resistance values of complexes Nos. 4 to 6 in powder pellets were as shown in Table 2.

[Table] Example 2 RhCl _{3.3H 2} O and 1.3 times the mole of 1, 4, 8,
11-Tetraazacyclotetradecane was dissolved in methanol and refluxed for 5 minutes. The produced yellow precipitate was allowed to cool, then separated, washed, and dried to obtain a rhodium salt complex. The obtained rhodium salt complex was dissolved in water, and to this aqueous solution was added dropwise an aqueous solution of lithium salt of 1.1 times the mole of tetracyanoquinodimethane. The generated precipitate was separated, washed with water, and dried to obtain a tetracyanoquinodimethane complex. The results are shown in Table 3. Example 3 Excess concentrated hydrochloric acid was added to the solution used to synthesize the rhodium salt complex in Example 2, and after separating the precipitates such as the HCl complex of 1,4,8,11-tetraazacyclotetradecane, the solution was passed through an evaporator. Concentrate with
Recrystallization was performed with a mixture of water and concentrated hydrochloric acid (3:1) to obtain the trans form of the rhodium salt complex. A tetracyanoquinodimethane complex was obtained from the obtained rhodium salt complex in the same manner as in Example 2. The results are shown in Table 3. Example 4 After adding an equimolar methanol solution of 1,4,8,11-tetraazacyclotetradecane to a methanol solution of CoCl ₂ .6H ₂ O, oxygen was bubbled through the solution for 1 hour. Then, when a small amount of concentrated hydrochloric acid was added, the solution turned dark green. Furthermore, after bubbling oxygen for 1 hour, the resulting precipitate was separated and the resulting liquid was concentrated using an evaporator and recrystallized from a small amount of water to obtain a cobalt salt complex. A tetracyanoquinodimethane complex was obtained from the obtained cobalt salt complex in the same manner as in Example 2. The results are shown in Table 3.

[Table] Example 5 A 1.1-fold mole hydrogen iodide aqueous solution was added to an ethanol solution of 1,4,8,11-tetraazacyclotetradecane, and the resulting precipitate was separated, washed with ethanol, and then dried. A 1.1-fold molar aqueous solution of lithium salt of tetracyanoquinodimethane was added dropwise to the obtained aqueous solution of ammonium salt. The generated precipitate was filtered, washed with water, and dried to obtain black granular crystals with a decomposition point of 173°C. The elemental analysis values of this crystal and the resistivity value of the powder pellets were as shown in Table 4.

【table】 [Brief explanation of drawings]

FIG. 1 shows electronic spectrum charts of tetracyanoquinodimethane complexes No. 1 to No. 3 obtained in Example 1, where the horizontal axis shows wavelength and the vertical axis shows intensity. 1: Electron spectrum chart of Cyc・N ²⁺ _i・TCNQ ^- ₂ (No. 1) 2: Electronic spectrum chart of Cyc・C ²⁺ _u・TCNQ ^- ₂・2H ₂ O (No. 2) 3: Cyc・Electronic spectrum chart of Z ²⁺ _o・TCNQ ^- ₂・H ₂ O (No. 3)

Claims (1)

[Claims] 1 General formula (Cyc) _l・mM ⁿ⁺ (TCNQ ^- ) _p・(TCNQ) _q・
Cl ^- _r・(sH ₂ O) _t (wherein, Cyc represents 1,4,8,11-tetraazacyclotetradecane; M represents hydrogen or nickel, copper, zinc, cobalt, manganese, palladium, rhodium and Represents a transition metal atom selected from lanthanum; TCNQ represents tetracyanoquinodimethane; l represents 1 or 2; m represents 1 to 4 when M is hydrogen; 1 when M is a transition metal atom;
n represents 1 to 3; p and q represent 0 to 4; r represents 0 to 2; s represents 1 or 2; t represents 0 or 1; ) Tetracyanoquinodimethane complex.