JPS6344566A - Novel tcnq complex - Google Patents

Abstract

NEW MATERIAL:A TCNQ complex containing 2-(fluoroalkyl)isoquinolinium cation expressed by formula I [R<1> is F, CF3, CH(CF3)2, CF(CF3)2 or (CF2)nCF3 (m is 1, 2 or 3); m is an integer of 2-7], 7,7,8,8-tetracyanoquinodimethane anion radical (TCNQ<tau>) and neutral TCNQ (TCNQ<omicron>) as constituent components. EXAMPLE:2-(4,4,4-Trifluorobutyl)isoquinolinium TCNQ complex. USE:An electrically conductive substance useful as electrically conductive materials expectable to provide various electrochemical or optical results and particularly effect of action excellent in heat resistance. PREPARATION:For example, a compound expressed by formula II utilizing reducing property of I<-> is reacted with neutral TCNQ at 3:4 molar ratio to readily afford the above-mentioned TCNQ complex.

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]

The 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, and TCNQ itself stacks up on its own. It exhibits high electrical conductivity due to its structural features.

TCNQ complexes have the advantages of light weight, anisotropy of conductivity, meltability, film-forming properties, ease of processing and molding, and other characteristic properties of organic compounds. Therefore, it can be used for applications in high-performance tetraelectric molecules, nonlinear optical materials, antistatic agents, molecular devices, biological devices, the design of highly ordered molecular assemblies with electronic functions, or electrolytic capacitors and batteries. It is a compound that is highly expected to be used in various fields of organic semiconductors, such as solid electrolytes.

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.

[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 TCNQ complex, which is an organic conductive compound and is expected to have various electrochemical or photochemical results.

(Structure of the Invention) [However, R1 is -F, -CF3. -CH(CF3)2
．． -(:F(CFs)z or -(CF2)nCF3 (
However, n represents an integer of 1 to 3. ), m is 2 to 7
indicates an integer. 2-(fluoroalkyl)isoquinolinium cation represented by
') and neutral TCNQ (TCNQ).

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, R1 of the isoquinolinium cation of the formula (rukyl) in the donor portion is -F.

-C:F3. -ell(CF3)2. -(:F(にF:
l) 2 or -(CF2). CF3 (where n represents an integer of 1 to 3); -(CI+2), m of -R represents an integer of 2 to 7;

The TCNiI body of the present invention can be easily obtained by a method known per se, for example, by a method of reacting with 2-(fluoroalkyl)isoquinolinium iodide 3:4 using the reducing property of iodo ion -. . 2-(fluoroalkyl)isoquinolium iodide is, for example, J,
Am, (:hem, soc,, 77°3637 (195
5); J, Org, Chem, 15,425 (19
49); J, Org.

Ghem, 21.748 (1956); Journal of the Society of Organic Synthetic Chemistry, 3A.

(to) 722 (197B) etc. can be easily obtained by reacting with isoquinoline in the presence of an appropriate solvent if necessary. It is sufficient to use what is obtained. Furthermore, it goes without saying that the TCNQ complex of the present invention can be similarly synthesized by a method in which a halide of a 2-(fluoroalkyl)isoquinolinium cation and TCN are obtained, and this is doped with neutral 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/fi. However, ρ is the specific resistance value (Ω
・cm), R is resistance (Ω), A is electrode contact area (cm)
''), j2 is the sample thickness (cm).Thermal properties can be measured by thermal analysis such as differential scanning calorimetry (DSC) 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. Synthesis of 1,1.1-trifluoro-4-iodobutane (Synthesis of ethyl 114,4,4-1-lifluorobutyrate 4
．． 4.41 Ethyl fluorocrotonate (manufactured by Aldrich) IOg (0.06 mol) was catalytically reduced at room temperature and pressure under a platinum oxide catalyst in ether, and the reaction solution was... After pA, the liquid was condensed in a liquid furnace, and the residue was distilled to give 7.8 g of a fraction with a bp of 126 to 129°C (ethyl 4,4,4-trifluorobutyrate).
was obtained as a colorless oil (yield 77%, GC content 98
．． 1%), (literature value) bp: 126-129°C [E, T
.

Mc13ee ej al,, J, Am, Ghem,
Soc, 72, 5071 (1950)].

(Synthesis of 214,4,4-trifluorobutanol (1)
) 7.5g of ethyl 4,4.4-trifluorobutyrate
The reaction was carried out under reflux for 6 hours. After the reaction, water was added to decompose excess LiA11 (4), and the residue obtained by concentrating the ether layer was distilled to obtain a fraction (4,4,4
-trifluorobutanol) 3.8 g were obtained as a colorless oil (yield 67%, GC content 98.5%).

(Literature value) bp: I24-125°C [tl, Ml
aiborskyet at,, J, Am, Chem
, Soc, 77.3637 (1955)].

(]) ]] 4,4,4-trifluorobutanol obtained in synthesis (2) of 1,1.1-trifluoro-4-dobutane3.
6g (0,028mat) to 18.6g potassium iodide
After reacting with 1.5 g of phosphoric acid 1 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 obtain a fraction with a bP of 125 to 127°C (1,
1,1-trifluoro-4-iodobutane) 3.3g
was obtained as a colorless oil (yield 50%, GC content 98
．． 9%).

(Literature value) b p ] I12-127℃ [tl, M,
Walborskyet at,, J, Am,
GhemySoc,, 77, 3637 (+955)]
.

'HNMR: δppm (CD 01 j) ■, 83~
2.50 (2H, m, CF3CII□C%CI+21
), 3.13~3.37 (411,m, (:F,C
1l, CH2ell, r).

Example 1. 2-(4,4,4-trifluorobutyl)
Synthesis of isoquinolinium TCNQ complex (1) Synthesis of 2-(4,4,4-trifluorobutyl)isoquinolinium iodide Isoquinoline [manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.] 820 mg (6
, 31111101) and Reference Example 1. 1, 1.1-
1.5 g of trifluoro-4-iodobutane (6,:
After heating and reacting 1 mmol 1) at 110 to 130°C for 3 hours, ethyl acetate was injected into the reaction solution to crystallize the target product, and the precipitation holes were removed and dried to obtain 1.46 g of a yellowish brown powder. yield 62.6%), mp: 147~
149.5℃.

Elemental analysis value ((as: +311+*hlN) calculated value:
0%41.4G, H%3.47. N%3.71 Actual value = C%41.32. H%3.56. N%3.
99゜'HNMR: δρpIIl(CDCj13◆D
MSO-d6)2.27~2.73 (411,1
11, y4cH2cycycF, s), 5.20 (2
H.

, J-7Hz, ':/NCj%CH2-),
7.90-9.13 (6H, rs.

isoquinoline ring hydrogen), 10.83 (IH,s, isoquinoline ring C5 hydrogen).

(2) 2-(4,4,4-t-lifluorobutyl)
Synthesis of TCNQ complex 0.98 g (4.8 mmol) of TCNQ (manufactured by Wako Tsumugi Kogyo) was dissolved in acetonitrile 50- by heating, and the 2-(4,4, 35rrL of an acetonitrile solution in which 1.32g of 4-trifluorobutyl)isoquinoliq)iodide was dissolved was added dropwise, and the mixture was heated under reflux for 1 hour.
Allowed time to react.

After the reaction, the reaction solution was cooled, the precipitation holes were removed, and recrystallization was performed from acetonitrile to obtain 1.22 g of blue-green needle crystals (yield: 78.4%).

Elemental analysis value [(hd(+7F3N5) (C+tlJ4
) 1.2] Calculated value 20% Ii8.64. H%
3. +9. H%19.91 Actual value = C%68.27
．． H%3.29. H%19.58゜Resistance value: 1
Ω・cm.

DSC: Endothermic point 210°C; exothermic decomposition point 263°C.

TCNQ'/TCNQ'' ratio = 1.19° Reference example 2.1
-Synthesis of fluoro-4-iodobutane 11) Synthesis of l-fluoro-4-bromobutane 1.4-dibromobutane [manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.] 154.8g (0.7:1m
ol) potassium fluoride in ethylene glycol 62.5
g (1.1 mol) and stirred at 100±10° C. for 7 hours. The reaction solution was injected into water, the resulting oil layer was separated, and this was distilled to obtain 28.2 g of a bp 133-134°C fraction (l-fluoro-4-bromobutane) as a colorless oil (yield: 25%).

(Literature value) b p : ] 334.2°C F, W, Ho
ffman, J. Org.

(:he+n,, +5.425 (1949)].

(2) Synthesis of l-fluoro-4-iodobutane In 100 ml of acetone, 26.3 g of l-fluoro-4-bromobutane obtained in (1) and 15.0 g of sodium iodide were reacted under reflux for 2 hours. The reaction solution was cooled, insoluble materials were removed, and the reactor solution was concentrated. Then, the 'a reduction residue was distilled under reduced pressure to obtain 17.2 g of a fraction (1-fluoro-4-iodobutane) with a bp of 60 to 62° C./20 nu++f1 g as a colorless oil (yield: 85.0%, GC content: 99 .2%)
. (Literature value) b p: 52.5-53.5°C/13+
rv+Hg [Tori, M, Pattison eL
al,, J, Org, (:hem,,
21°748 (1956)].

'HNMR: δPP0I (CD C23) 1.80~
2.20 (4H, m, CFII2GHzCH, Glh
l), 3.07-3.5:1 (411, m, CFj
j, [:H□(:1hcH,I).

Example 2 Synthesis of fil 2-(4-trifluorobutyl)isoquinolinium iodide Isoquinoline [manufactured by Wako Pure Chemical Industries Ltd.] 6.5 g (50
mmol) and 1-fluoro-4- obtained in Reference Example Z.
Iodobuta:, Z Io, 1g (50mmol) 5
After reacting with stirring at 5 to 65°C for 1 hour, acetone was poured into the reaction solution to crystallize the target product, and the precipitated crystals were collected and dried to obtain 9.4 g of a yellow powder (yield: 56 .8%), m
p: 135 total p value: 0%47.15.8%4.57.
N%4.23 Actual value = C%46.82.8%4.92
．． N%4.48゜'HNMR: δppm (CD C
R3+ DMSO-ds) 1.80-2.57 (
4H,m,;N-co□(:%CjiCH2F),
3.30(2H,t, J-611z,;N(
lhC) I□C1h(:II,F), 5.15 (211
゜Shi, J=7Hz, ,”N-CH2-), 7.
87-9.17 (61 (,10, inquinoline ring hydrogen)
, 10.83 (IH,s, inquinoline ring C1 hydrogen)
.

[212-(4-fluorobutyl) inquiturium TC]
Synthesis of NQ complex 3.27 g (16 m+IIol) of TCNQ [manufactured by Wako Pure Chemical Industries, Ltd.] was dissolved by heating in 150 rnl of acetonitrile, and 3.98 g of 2-(4-fluorobutyl)isoquinotium iodide obtained in (1) was dissolved therein. 100 m7 of the dissolved acetonitrile solution was added dropwise and reacted under reflux for 1 hour. The reaction solution was cooled, the precipitated crystals were collected, and recrystallized from acetonitrile to obtain 3.16 g of black-purple needle crystals (yield: 64.4%).

Elemental analysis value ((as: 37823FN9) calculated value 2C
%72.54. H%3.7B, N%20.58Actual value=C%72.29.8%4.03. N% 20.82
゜Specific resistance value: 5Ω・cm.

DSC: Endothermic point 217°C: Exothermic decomposition point 218°C.

TCNQ7TCNQ” ratio = 1.000 Furthermore, neutral TCN
Q (denoted as TCNQ') and anion radical TCNQ (
complex composition ratio (represented as rcNQ'/Tc
Nq”) is based on literature (A, I (embaum et al.
,.

J, 8rn, Chem, Soc,, 93.253
2 (+971)) by 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+++) was determined based on the above calculation formula. Ta.

〔Effect of the invention〕

As stated above, the present invention is characterized in that a 2-(fluoroalkyl)isoquinolinium cation, which has not been used in TCNQ complexes, is used as a donor, and various electron It has a remarkable effect in that it can provide a new TCNQ complex that can be expected to produce chemical or 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 other effects and contribute to this industry.

Patent applicant Wako Pure Chemical Industries, Ltd. July 2, 1986 1. Case description 1988 Patent Application No. 188182 2, Title of Invention New TCNQ Complex Contact Information Patent Division (Tokyo) Address: 03-270-8571
4. Date of the amendment order. 5. Detailed description of the invention in the specification to be amended.

6. Contents of correction "Endothermic point 210℃" written on page 15 of old specification IO
” is corrected to “endothermic point 232°C”.

(2) “Exothermic decomposition point 26” stated on page 10, line 15 of the specification
3℃" is corrected to "exothermic decomposition point 272℃."

(3) "4-trifluorobutyl" written on page 12, line 3 of the specification is corrected to "4-fluorobutyl."

that's all Procedural amendment February 27, 1986 1. Display of incident 1985 Patent No. 188182 2 Name of invention New 'l'cNQ complex 1. Person making the amendment Relationship to the case Patent applicant Communication device 03-270-8571 4. Date of amendment order 5. Subject of correction Detailed description of the invention in the specification.

6. Contents of amendment (1) "C17HJN stated in page 10, line 11 of the specification"
4) Correct J to "(C72H4N4)".

(2) "Nψ-CH2-" described on page 12, line 18 of the specification
j is corrected as r>No-C.

that's all

Claims (1)

[Claims] Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^1 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. ] 2-(fluoroalkyl)isoquinolinium cation represented by 7, 7,
8,8-tetracyanoquinodimethane anion radical (
A TCNQ complex comprising TCNQ^-) and neutral TCNQ (TCNQ^-) as constituent components.