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

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、停電性材料等として有用な新規ＴＣＮＱ錯体
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel TCNQ complex useful as a blackout material, etc.

〔発明の背景〕[Background of the invention]

ＴＣＮＱ錯体は、有機半導体として知られる電荷移動型
錯化合物であり、その構成成分であるＴＣＮＱが電子を
受は入れ易く、陽イオンと極めて安定なラジカル塩を作
り、ＴＣＮＱ自身か独自に禎み１ｎなるといつ構造的特
徴を有することに起因して高導電性を示す。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.

Ｔ　ＣＮ　Ｑ　２ｒｔ体は、軽ｈ：、電導の異方性、溶
融ｆ［、フィルム形成＋１．加Ｖ及び成形の容易さ等、
１１機化合物のもつ特徴的性７′【と金属の性質を併せ
１）−１−るという有利な点を有し、このム、高機能Ｊ
、ｑ電士１分子膜、非線形光学材料、帯電防止剤、分子
′−素ｒ−９牛物素ｒ−への応用、電を機能をもつ高枕
ｊ？−分子集合体の設語に、或は電解コンデンサや１に
池の国体電解′ｉ１等、様々な仔機半専体分野に、その
利用が大いに期待されている化合物である７、 ＴＣＮＱ錯体に関しては、これまでに多数の含や素複素
糧化合物カチオンＴＣＮＱ錯体が合成さ九ているが、本
来ＴＣＮＱ錯体は有機化合物であり、置換Ｊ、（や構成
している元素を代えることによってわずかずつ構造や性
質を変化させ一〇いくことかできるので、これによって
導電体として請求される様々な付合の最適化を［Ｉ的に
応じてはかることがｉ’Ｔ能なため、それら各種ニーズ
に対応し１７る史に新たなＴＣＮＱ錯体の開発が望まれ
ている。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.

〔発明の目的〕[Purpose of the invention]

本発明は、ト記した如き現状に鑑みなされたもので、有
機導電性化合物であり、種々の電子化学的、或は光化学
的成果が期待できる新規なＴＣＮＱ錯体を提供すること
を目的とする。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.

〔発明の構成〕[Structure of the invention]

（但し、１（１は分枝鎖を４Ｔする炭素数４〜６のアル
キル基を示す。）で表わされるＮ−置換イツキノリニウ
ムカチオンと、　７，７，８．８−テトラシアノキノシ
メタンアニオンラシカル（ＴＣＮＱ’）及び中性ＴＣＮ
Ｑ　（ＴＣＮＱ’）とを構成成分とするＴＣＮＱ錯体の
発明である。(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.

本発明のＴＣＮＱ錯体は、例えば下記の如く表わされる
。The TCNQ complex of the present invention is represented, for example, as follows.

（式中、ｋは０．５≦に≦２．０なる任意の数を表ね−
１−５、） 本発明のＴＣＮＱ錯体に於て、ドナ一部の式ニウムカチ
オンの１（１としては、例えば、　１ｓｏ−ブチルＪ、
Ｌ、５ｅＣ−ブチル基、２−メチルブチル基、＋ＳＯ−
アミル基、２，２−ジメチルプロピル基、；１．３−ジ
メチルブチル基、２−メチルペンチル基、３−メチルペ
ンチル基等、分枝３ｎを打する炭素数４〜６のアルキル
Ｊ、ｔ、か挙げられる。(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.

本発明のＴＣＮＱ錯体は、自体公知の方法、例えばＮ−
置換イツキノリニウムカチオンのハロゲン化物とＴＣＮ
ＱのＬｉ塩とを反応させてをドーピングさせる方法によ
り容易に合成しｊ″：？る１、Ｎ−置換イツキノリニウ
ムカチオンのハロゲン化物は、例えば、化合物Ｘ−Ｒ’
（式中、Ｘはば適当な溶媒の存在下イソキノリンと反応
させることにより容易に得ることができるので、この様
にして得たものを用いることで足りる。化合物Ｘ−Ｒ’
は、例えばＪ、Ａｍ、（：ｈｅｍ、ｓｏｃ、、８９．１
１３５（１９６７）等に記載の方法に準じて、対応する
アルコール類とアルカリ金属ハライドとを反応させるこ
とにより容易に得ることかできるので、この様にして得
られたものを用いることで足りる。また、本発明のＴ　
ＣＮ　Ｑ　ｉｆｆ体は、ヨードイオン　ドの還元力を利
用し、Ｎ−置換イツキノリニウムカチオンのモル比３：
４で反応させる方法によっても同様に合成し得ることは
言うまでもない。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.

合成された本発明のＴＣＮＱ錯体は、電荷移動錯体特有
の色や電荷移動吸収帯の出現によって識別することがで
き、錯体組成比は元素分析及び紫外線吸収スペクトルの
測定から決定することができる。電気的性質、例えば比
抵抗値は、試料粉末をペレットに成型し二端子法て電流
電圧を測定して抵抗値Ｒを算出し、次式から求めること
ができる。ｐ＝Ｒ−Ａ／ｆｆｉ。但し、ρは比抵抗値（
Ω・ｃｍ）、Ｒは抵抗（Ω）、Ａは電極接触面積（シバ
）、ｌは試料の厚さくｃｍ）である。また、熱的ｆ’ｌ
質は、示差走査熱１ｉｔ（ＤＳＣ）測定等の熱分析て４
１１１定することかできる。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.

本発明の新規なＴＣＮＱ錯体は、特にその単独又は混合
品の４電性、加工及び成形性及び耐熱性に（廿れている
ので、これを高機能導電性分子膜、切線形光学材料、こ
れらの分子−素子、生物素子への応用なと電子機能をも
つ高秩序分子集合体の設、１１に、或は電解コンデンサ
や電池の固体電解質として等様々な打機半４体分野に於
て有効に用いＴｌることが期待できる。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.

以ドに実施例及び参考例を示すが、本発明はこれら実施
例、参考例により何等制約を受けるものではない。Examples and reference examples are shown below, but the present invention is not limited in any way by these examples and reference examples.

（実施例） ｔＪ例１．１−ヨード−３，３−ジメチルブタンの合成
３．３−ジメチルブタノール（和光純薬工業■製）１０
ｇ　（９２ミリモル）をヨウ化カリウム７４．４ｇ及び
リン酸５４ｇと１３時間還流反応させた。冷却後反応液
を水１００ｄ中に注入し、エチルエーテル１００１ｒＬ
ｌで抽出した。エーテル層を５％亜硫酸ナトリウム水溶
液で１回、水で３回洗浄後、無水Ｍｇ５Ｏ，で乾燥し、
脱水剤枦去後、溶媒留去し、残渣の橙黄色油状物を減圧
蒸留してｂｐ５６〜５８℃／２０ｍｍｆ１ｇ留分１８．
５ｇを微黄色油状、物として得た（収率８９．１％）。(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。'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）。-(:(C113)3), 1.75~2.03(21
1,m,-CH,01121) , :3.02~3J2
(2H,Ill, -(:H211:IIXI).

参考例２〜４．各種１−ヨードアルカンの合成市販の種
々のアルコール類を用いて参考例１と同様に反応及び後
処理を行い、表−１に示す如きｌ−ヨードアルカンを得
た。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.

・へ４例５．１−ヨードー２，２−ジメチルプロパンの
合ノ・ｋ （１）ｐ−トルエンスルホン酸２，２−ジメチルプロピ
ルエステルの合成 ２．２−ジメチルプロパツール２５ｇ　　（０，２８モ
ル）とピリジン　１２０ｒＬＬｌの混合液にｌＯ℃以−
トでＰ−１ルエノスルホニルクロライド５９．５Ｋ　　
（０，：１１モル）を滴トし、２０〜２５℃て１時間撹
拌反応させた。反応液をＩｌ（：Ｉ（１０ｍｌ中に１ｈ
人し、エチルエーテル１００ｍ／で抽出してニーデル層
を水で２回洗浄した。無水％ＴｇＳ１１４で乾燥後、脱
水剤を枦去し、溶媒を留去して残渣５７ｇのシナ色油状
物としてＩＩだ（収率　８２．９％）。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。'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）。-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）１−ヨード−２，２−ジメチルプロパンの合成ｉ
ｌｌで得たＰ−トルエンスルホン酸２，２−ジメチルプ
ロピルエステル５３．３ｇ（０，２２モル）をエチルセ
ロソルブ１５０　ｍｌ中、ヨウ化ナトリウム６６ｇと還
流下２時間反応させた。冷却後、反応液を水２００　ｍ
ｌ中に注入し、石油エーテル１００ｒｎ！で２回抽出し
て石油エーテル層を水で２回洗浄した。(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.

無水ＭｇＳＯ４で乾燥し、脱水剤をか人後溶媒留去し、
残液の黄色油状物を減圧蒸留してｂｐ’７５〜７８℃／
１３０〜Ｉ：Ｉ５ｍｍＨｇ留分２１．５ｇを無色油状物
として得た（収率　４９．３％）。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。'HN M Rδppm (CD Ci! 3): l
, 05 (911,S.

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

参考例６．　Ｎ−（３，３−ジメチルブチル）イソキノ
リニウムアイオダイドの合成 イソキノリン６．５ｇ　（５０ミリモル）と参考例１で
得た１−ヨード−３，３−ジメチルブタンＩＯ，６ｇ（
５０ミリモル）を１００〜１１０℃で３０分撹拌反応さ
せた後冷却して固化させた。次いで固化した反応物をア
セトン−エタノールより再結晶し、黄色結晶９．５ｇを
得た（収率　５５．３％）。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℃。m　p　180-181℃.

！しＪ１分析イ直（Ｃ１５Ｈｉｎ　　Ｉ　　Ｎ）工甲論
ずｌｌ’ｌ　　（ｆｉ）　　　Ｃ：　　５２．１１０．
Ｈ：　　５．９１．　　　Ｎ　　：　　４．１０天ｄｊ
ｌｌ　イ〆）（’に）　　　Ｃ：　　５２．６６、Ｈ：
　　６．０７．　　Ｎ　　：　　４．２！１　。! 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　　（旧！、Ｓ。'HNMRδPI)m (GDIJ,): 1
．． 07 (old!, S.

−１車旧）＋＋）　、　１．！１２．〜２．２０（２Ｎ
、　ｍ、　’；Ｎ”に１１２ｃｌ！２−）　。-1 car old)++), 1. ! 12. ~2.20 (2N
, m, ';N'' to 112cl!2-).

１　、Ｉｌ’、ｔ〜５　、口（２１１，ｍ、　７Ｎ”１
−ＨＪ−）　、　７．ｈ：Ｊ〜８．９０（［ｉｌｌ。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。m, 1soquinolinc -C,, ~C1
1), 10.93 (III, s.

１°）ｃ＋＋１ｕｉｎｏｌｉｎｅ　−Ｃ１３゜１；乙例
７〜１４．Ｎ−アルキルイソキノリニウムハづイトの合
成 葛ち例２〜４で１１また各柿ｌ−ヨードアルカンスはｌ
−ブロム−４−メチルペンタン（東京化成４〜嬰）とイ
ソキノリンとを参考例６と同様に反応さけ対応″Ｊ−る
Ｎ−アルキルイソキノリニウムハラ１′トを得た。結果
を表−２（１）及び（２）に示′４−６以トキ白 ３考例１５．ＴＣＮＱ　　Ｌｉ塩の合成Ｔ　ＣＮ　Ｑ　
　２０．４ｇ（０，１モル）をアセトニトリル１．５　
Ｑに加湿溶解し、これにヨウ化すチウムハ、ξＩｇ１０
．２モル）をアセトニトリル２００ｒｒＬ！に溶解した
溶液を滴下して５流ド１時間反応させた。反１１−、イ
（、冷却して結晶を枦取し、乾燥して紫色粉末＋！ｉ＋
　２０　、　Ｑｇを得た（収率　９４．８％）。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%).

実施例１．Ｎ−（４−メチルペンチル）イソキノリニウ
ムＴＣＮＱ中−塩の合成 写考例１３で１１＋られたＮ−（４−メチルペンチル）
イソキノリニウムブロマイド２．９４ｇを参考例１１１
でミリられたＴＣＮＱのＬｉ塩２．１１ｇ　（１０ミリ
モルンを溶解したメタノール溶／＆　１２０ｒｎｌ中に
加え、連流ト２時間反応させた。反応後、反応液を冷却
して（ハ出品を枦取し、洗浄、乾燥してＮ−（４−メチ
ルペンチル）イソキノリニウムＴＣＮＱ単塩’Ｉ　、　
４０　ｇを＋’ｆ紫色粉末として得た（収率　旧、２％
）。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、＋、分析値（Ｃ２７Ｈ２４Ｎ　５）理論ｆＩＩＩ
＋（ネ）　Ｃニア７．４９．　Ｈ：　５．７Ｂ、　Ｎ：
　１６．７４１′犬Ｚ則イ直（％）　　Ｃニア７．４５
．　　Ｈ：　　５．８６．　　Ｎ：　　１６．６９゜Ｄ
ＳＣ：吸熱点１７０℃；発熱分解点２４８℃。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.

実ｈ６例２．Ｎ−（４−メチルペンチル）イソキノリニ
ウムＴＣＮＱ錯体の合成 実ｈ’ｔｈ例１で得られたＮ−（４−メチルペンチル）
イソキノリニウムＴ　ＣＮ　Ｑ　ｌ１ｌ−塩２．０９ｇ
　　（５ミリモル）とＴＣＮＱｌ、０２ｇ　（５ミリモ
ル）をアセトニトリル２００ｄに加温溶解し、速流下２
時間反応させた。反応後、冷却して結晶を枦取し、アセ
トニトリルよりｍ結晶してＴＣＮＱ錯体２．１４ｇを黒
紫色針状晶として得た（収率　６８．８％）。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%).

元素分析値（Ｃ３９Ｈ２８Ｎ　Ｏ） 理論値（９６）　Ｃニア５．２２．　Ｈ：　４．５３．
　Ｎ　：　２０．２４実測値（９６）　Ｃニア５．３０
．　Ｈ：　４．５６．　Ｎ：　２０．＋４゜比抵抗値：
２Ω・ｃｍ。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：吸熱点２１８℃；発熱分解点２７１℃。DSC: Endothermic point 218°C; exothermic decomposition point 271°C.

ＴＣＮＱ’／ＴＣＮＱ′：比：　ｉ　、ｏｏ。TCNQ'/TCNQ': Ratio: i, oo.

実施例３．８−（３，３−ジメチルブチル）イソキノリ
ニウムＴＣＮＱ錯体の合成 アセトニトリ／ｌ／　１５０ｍ１ニＴ　ＣＮ　Ｑ　３．
０６ｇを加温溶解し、これに参考例６で得られたＮ−（
３，３−ツメチルブチル）イソキノリニウムアイオダイ
ドｉ、ｌ１４ｇを溶解したアセトニトリル溶液を滴下し
て１時間５流を行った。冷却後、析出した結晶を２１’
取し、アセトニトリルより再結晶してＴＣＮＱ２ｆ？体
３．６４ｇを黒紫色針状晶として得た（収率ン１１．Ｕ
％）。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).
%).

元素分析値（Ｃａｔ＋Ｈ２ｎＮ　９） Ｉ１１１１ｉｉイＩＩＩ＋　（！ｌｉ）　　　Ｃニア５
．２２．　　　Ｈ：　　４．５３．　　　Ｎ　　：　　
２０．２４実測値（％）　Ｃニア５．＋９．　Ｈ：　４
．６６、　Ｎ：　２０．１５゜比抵抗値：２Ω・ｃｍｏ ＤＳＣ：吸熱点２２２’Ｃ；発熱分解点２７６℃。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　”比：１．旧。T　CN　Q　/T　CN　Q　” ratio: 1. Old.

実施例４〜ＩＯ，ＴｃＮ−Ｑ錯体の合成鴬考例７〜１２
及び１４で得られた各種Ｎ−アルキル−ｒツキノリニウ
ムアイオダイドを用いて、実施例３と同様に反応及び後
処理を行い、対応するＴＣＮＱ錯体を得た。結果を表−
３（１）及び（２）に小ず。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.

面、中＋ＥＴＣＮＱ　（ＴＣＮＱ’と表示）とアニオン
ランカルＴＣＮＱ　（ＴＣＮＱ”と表示）との錯体構成
比（’Ｉ’Ｃ＋ＩＱ　”／１’（：Ｎ１７勺は文献（Ａ
、ｌｌｅｍｂａｕｍ　ｅＬ　ａｌ、。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））に従い紫外線吸収スペクトル
社！１１定方法で求めた。また、吸ジさ点及び発熱分解
点については示差走査熱計（ｏｓＣ）測定で求めた。電
気的特性値について仁［錯体をベレットとし、以ド常法
に従って試料１つ製の接２５°Ｃで電流電圧測定（二端
子法）を行い、１１１１記計算式にＪ、ｔｊ−５いて比
抵抗値ρ（Ω・ｃｍ　）を求めた。, 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.

〔発明の効果〕〔Effect of the invention〕

以ト述べた如く、本発明は、これまでＴＣＮＱｌｌ一体
に用いられていなかったＮ−置換イツキノリニウムカチ
オンをドナーとして用いた点に特徴をｆｌするイｌ明で
あり、従来にない種々の電子化学的或は光学的成果か期
待できる新規なＴＣＮＱ錯体を提供し得るものである点
に顕著な効果を奏するものであり、斯業に貢献するとこ
ろ大なる発明である。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)

【特許請求の範囲】 式 ▲数式、化学式、表等があります▼ （但し、Ｒ＾１は分枝鎖を有する炭素数４〜６のアルキ
ル基を示す。）で表わされるＮ−置換イソキノリニウム
カチオンと、７、７、８、８−テトラシアノキノジメタ
ンアニオンラジカル（ＴＣＮＱ＾■）及び中性ＴＣＮＱ
（ＴＣＮＱ＾■）とを構成成分とするＴＣＮＱ錯体。[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.