JPS63188657A - Novel tcnq complex - Google Patents

Abstract

NEW MATERIAL:The complex containing an N-substituted isoquinolinium cation of formula (R<1> is branched 4-6C alkyl), 7,7,8,8-tetracyanoquinodimethane anion radical and neutral TCNQ as constituent components. USE:An electrically conductive material. It has excellent electrical conductivity, processability, moldability and heat-resistance and useful in the field of various organic semiconductors such as high-performance electrically conductive membrane, non-linear optical material, their application to molecular element, bioelement, etc., and the design of highly ordered molecular assembly having electronic function, etc. PREPARATION:The objective TCNQ complex can be produced by reacting a halogenated N-substituted isoquinolinium cation of formula (R' is branched 4-6C alkyl) with Li salt of TCNQ and doping neutral TCNQ to the reaction product.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel TCNQ complex useful as a blackout material, etc.

[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. When this happens, it exhibits high electrical conductivity due to its structural features.

The T CN Q 2rt body has light h:, anisotropy of conductivity, melting f[, film formation +1. Added V and ease of molding, etc.
This compound has the advantage of combining the characteristic properties of 11-organic compounds with the properties of metals.
, q-density single molecule film, nonlinear optical material, antistatic agent, application to molecule'-element r-9 and cattle element r-, Takamakura j? with electric function? - Concerning the TCNQ complex, which is a compound that is highly expected to be used as a term for molecular assemblies, or in a variety of semi-dedicated fields such as electrolytic capacitors and national electrolysis. Although a large number of cationic TCNQ complexes of complex compounds have been synthesized so far, TCNQ complexes are originally organic compounds, and the structure can be changed little by little by substitution, (or by changing the constituent elements). Since it is possible to change the properties and properties of the conductor in a number of ways, it is possible to optimize the various combinations required as a conductor. The development of new TCNQ complexes has been desired for the past 17 years.

[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, N-substituted quinolinium cation represented by 1 (1 indicates an alkyl group having 4 to 6 carbon atoms with a 4T branched chain) and 7,7,8.8-tetracyanoquinosimethane Anionic radical (TCNQ') and neutral TCN
This is an invention of a TCNQ complex having Q (TCNQ') as a constituent component.

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

(In the formula, k represents any number that satisfies 0.5≦≦2.0.
1-5,) In the TCNQ complex of the present invention, some of the donor nium cations include 1 (1, for example, 1so-butyl J,
L, 5eC-butyl group, 2-methylbutyl group, +SO-
Amyl group, 2,2-dimethylpropyl group,; 1,3-dimethylbutyl group, 2-methylpentyl group, 3-methylpentyl group, etc., alkyl J having 4 to 6 carbon atoms with branch 3n, t, Can be mentioned.

The TCNQ complex of the present invention can be prepared by methods known per se, for example N-
Substituted quinolinium cation halides and TCN
A halide of a 1,N-substituted quinolinium cation easily synthesized by a method of doping by reacting with a Li salt of Q is, for example, a compound X-R'
(In the formula, X can be easily obtained by reacting with isoquinoline in the presence of an appropriate solvent, so it is sufficient to use the product obtained in this way. Compound X-R'
For example, J, Am, (:hem, soc, , 89.1
135 (1967) etc., by reacting the corresponding alcohol with an alkali metal halide, it is sufficient to use the product obtained in this way. In addition, the T of the present invention
The CN Qiff form utilizes the reducing power of the iodo ion, and the molar ratio of the N-substituted quinolinium cation is 3:
It goes without saying that it can be similarly synthesized by the reaction method in step 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 values, can be determined from the following equation by molding sample powder into pellets, measuring current and voltage using a two-terminal method, and calculating resistance value R. p=RA/ffi. However, ρ is the specific resistance value (
R is the resistance (Ω), A is the electrode contact area (cm), and l is the sample thickness (cm). Also, thermal f'l
The quality is determined by thermal analysis such as differential scanning calorimetry (DSC) measurement.
111 can be determined.

The novel TCNQ complex of the present invention has particularly good tetraelectricity, processing and moldability, and heat resistance when used alone or as a mixture. It is effective in various fields such as application to molecular devices, biological devices, the construction of highly ordered molecular aggregates with electronic functions, or as solid electrolytes for electrolytic capacitors and batteries. It can be expected that Tl will be used for this purpose.

Examples and reference examples are shown below, but the present invention is not limited in any way by these examples and reference examples.

(Example) tJ Example 1. Synthesis of 1-iodo-3,3-dimethylbutane 3.3-dimethylbutanol (manufactured by Wako Pure Chemical Industries, Ltd.) 10
g (92 mmol) was reacted under reflux with 74.4 g of potassium iodide and 54 g of phosphoric acid for 13 hours. After cooling, the reaction solution was poured into 100 d of water, and 1001 rL of ethyl ether was added.
Extracted with l. The ether layer was washed once with a 5% aqueous sodium sulfite solution and three times with water, then dried over anhydrous MgO,
After removing the dehydrating agent, the solvent was distilled off, and the remaining orange-yellow oil was distilled under reduced pressure to obtain fraction 18.
5 g of a pale yellow oil was obtained (yield: 89.1%).

'HNMR: δppm (CDα3): 0.90 (
9H,s.

-(:(C113)3), 1.75~2.03(21
1,m,-CH,01121) , :3.02~3J2
(2H,Ill, -(:H211:IIXI).

Reference examples 2 to 4. Synthesis of various 1-iodoalkanes Using various commercially available alcohols, reactions and post-treatments were carried out in the same manner as in Reference Example 1 to obtain 1-iodoalkanes as shown in Table 1.

4 Example 5. Synthesis of 1-iodo-2,2-dimethylpropane (1) Synthesis of p-toluenesulfonic acid 2,2-dimethylpropyl ester 2.2-dimethylpropane 25 g (0.28 mol) ) and pyridine at 10℃ or higher.
P-1 luenosulfonyl chloride 59.5K
(0,:11 mol) was added dropwise to the mixture, and the mixture was stirred and reacted at 20 to 25°C for 1 hour. The reaction solution was mixed with Il (:I (in 10 ml for 1 h)
The mixture was extracted with 100ml of ethyl ether, and the needle layer was washed twice with water. After drying with anhydrous % TgS114, the dehydrating agent was removed and the solvent was distilled off to leave a residue of 57 g of a light brown oil (yield: 82.9%).

'HN M Rδppm (CD C23): 0.8
7 (9+1.S.

-I: ([:1h)1), 2.4:l (:Il!,
s, Q-cHJ, :J, 65 (211°s, -50
1Clll-), 7.2:I ~7.113(411
, +n, aromatic If).

(2) Synthesis of 1-iodo-2,2-dimethylpropane i
53.3 g (0.22 mol) of P-toluenesulfonic acid 2,2-dimethylpropyl ester obtained in Example 1 was reacted with 66 g of sodium iodide in 150 ml of ethyl cellosolve under reflux for 2 hours. After cooling, the reaction solution was poured with 200 m of water.
100rn of petroleum ether! The petroleum ether layer was extracted twice with water and washed twice with water.

Dry with anhydrous MgSO4, remove the dehydrating agent, and then remove the solvent.
The residual yellow oil was distilled under reduced pressure to bp'75-78℃/
130-I: 21.5 g of I 5 mmHg fraction was obtained as a colorless oil (yield 49.3%).

'HN M Rδppm (CD Ci! 3): l
, 05 (911,S.

-C(CTo)3)J,I5 (211,s, -(:
H21).

Reference example 6. Synthesis of N-(3,3-dimethylbutyl)isoquinolinium iodide 6.5 g (50 mmol) of isoquinoline and 6 g of 1-iodo-3,3-dimethylbutane IO obtained in Reference Example 1 (
50 mmol) was stirred and reacted at 100 to 110° C. for 30 minutes, and then cooled and solidified. The solidified reaction product was then recrystallized from acetone-ethanol to obtain 9.5 g of yellow crystals (yield: 55.3%).

m　p　180-181℃.

! C15Hin I N Kokoronzull'l (fi) C: 52.110.
H: 5.91. N: 4.10 dj
ll I〆) ('に) C: 52.66, H:
6.07. N: 4.2!1.

'HNMRδPI)m (GDIJ,): 1
．． 07 (old!, S.

-1 car old)++), 1. ! 12. ~2.20 (2N
, m, ';N'' to 112cl!2-).

1, Il', t~5, mouth (211, m, 7N"1
-HJ-), 7. h: J~8.90 ([ill.

m, 1soquinolinc -C,, ~C1
1), 10.93 (III, s.

1°) c++1uinoline -C13°1; B Examples 7 to 14. In Examples 2 to 4, each persimmon l-iodoalcanth is l
-Bromo-4-methylpentane (Tokyo Kasei 4-Year-Old) and isoquinoline were reacted in the same manner as in Reference Example 6 to obtain a corresponding "N-alkylisoquinolinium halide 1'. The results are shown in the table below. Example 15. Synthesis of TCNQ Li salt TCNQ
20.4g (0.1 mol) of acetonitrile 1.5
Humidified and dissolved in Q, iodine, ξIg10
．． 2 moles) to 200rrL of acetonitrile! A solution dissolved in water was added dropwise to the solution and reacted for 1 hour in 5 streams. Anti-11-, I (, Cool, remove the crystals, dry and turn into a purple powder +!i+
20, Qg was obtained (yield 94.8%).

Example 1. Synthesis of N-(4-methylpentyl) isoquinolinium TCNQ salt
Reference Example 111: 2.94 g of isoquinolinium bromide
2.11 g of Li salt of TCNQ (10 mmol) was added to 120 rnl of methanol solution dissolved in it, and reacted for 2 hours in continuous flow. After the reaction, the reaction solution was cooled and , washed and dried to obtain N-(4-methylpentyl)isoquinolinium TCNQ monosalt 'I.
Obtained 40 g as +'f purple powder (yield old, 2%
).

lL, +, analytical value (C27H24N 5) theory fIII
+(ne) C near 7.49. H: 5.7B, N:
16.741' Dog Z rule I direct (%) C near 7.45
．． H: 5.86. N: 16.69°D
SC: Endothermic point 170°C; exothermic decomposition point 248°C.

Actual h6 example 2. Synthesis of N-(4-methylpentyl)isoquinolinium TCNQ complex N-(4-methylpentyl) obtained in h'th Example 1
Isoquinolinium T CN Q l1l-Salt 2.09g
(5 mmol) and TCNQl, 02 g (5 mmol) were dissolved in 200 d of acetonitrile while heating, and
Allowed time to react. After the reaction, the reaction mixture was cooled, the crystals were collected, and crystallized from acetonitrile to obtain 2.14 g of TCNQ complex as black-purple needle crystals (yield: 68.8%).

Elemental analysis value (C39H28N O) Theoretical value (96) C near 5.22. H: 4.53.
N: 20.24 actual value (96) C near 5.30
．． H: 4.56. N: 20. +4゜specific resistance value:
2Ω・cm.

DSC: Endothermic point 218°C; exothermic decomposition point 271°C.

TCNQ'/TCNQ': Ratio: i, oo.

Example 3. Synthesis of 8-(3,3-dimethylbutyl)isoquinolinium TCNQ complex Acetonitrile/l/150ml 2TCNQ 3.
06g was dissolved by heating, and to this was added the N-( obtained in Reference Example 6).
An acetonitrile solution containing 14 g of 3,3-trimethylbutyl)isoquinolinium iodide i was added dropwise in 5 streams for 1 hour. After cooling, the precipitated crystals were
Then, recrystallize from acetonitrile to obtain TCNQ2f? 3.64 g of the compound was obtained as black-purple needle crystals (yield: 11.U).
%).

Elemental analysis value (Cat+H2nN 9) I1111iiiii+ (!li) C near 5
．． 22. H: 4.53. N:
20.24 Actual value (%) C near 5. +9. H: 4
．． 66, N: 20.15° Specific resistance value: 2Ω・cmo DSC: Endothermic point 222'C; exothermic decomposition point 276°C.

T　CN　Q　/T　CN　Q　” ratio: 1. Old.

Example 4 - Synthesis of IO, TcN-Q complex Examples 7 to 12
Using various N-alkyl-rtsuquinolinium iodides obtained in 1 and 14, reactions and post-treatments were carried out in the same manner as in Example 3 to obtain corresponding TCNQ complexes. Display the results -
3 (1) and (2) with a small amount.

The complex composition ratio ('I'C+IQ ''/1' (:N17 is based on the literature (A
, llembaum eL al.

, 1 ^m, [:hc+n, 5(Ic,, 91.
2532 (1971)), Ultraviolet Absorption Spectrum Inc.! It was determined using the 11-determined method. In addition, the suction point and exothermic decomposition point were determined by differential scanning calorimetry (osC) measurement. Regarding the electrical characteristic values, using the complex as a pellet, current-voltage measurements (two-terminal method) were made using a single sample at 25°C according to the usual method, and J and tj-5 were calculated using the formula 1111. The resistance value ρ (Ω·cm ) was determined.

〔Effect of the invention〕

As described above, the present invention is characterized in that it uses N-substituted quinolinium cations as donors, which have not been used in TCNQll until now. This invention has a remarkable effect 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.

Claims (1)

[Claims] N-substituted isoquinolite represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (wherein R^1 represents a branched alkyl group having 4 to 6 carbon atoms) cation, 7,7,8,8-tetracyanoquinodimethane anion radical (TCNQ^■) and neutral TCNQ
A TCNQ complex containing (TCNQ^■) as a constituent component.