JPH0684352B2 - Novel TCNQ complex - Google Patents
Novel TCNQ complexInfo
- Publication number
- JPH0684352B2 JPH0684352B2 JP15949586A JP15949586A JPH0684352B2 JP H0684352 B2 JPH0684352 B2 JP H0684352B2 JP 15949586 A JP15949586 A JP 15949586A JP 15949586 A JP15949586 A JP 15949586A JP H0684352 B2 JPH0684352 B2 JP H0684352B2
- Authority
- JP
- Japan
- Prior art keywords
- tcnq
- complex
- tcnq complex
- novel
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 title claims description 30
- 230000007935 neutral effect Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- -1 radical salt Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VFFVKDVUBDDHHS-UHFFFAOYSA-M 1-butyl-2-phenylpyridin-1-ium;iodide Chemical compound [I-].CCCC[N+]1=CC=CC=C1C1=CC=CC=C1 VFFVKDVUBDDHHS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、導電性材料等として有用な新規TCNQ錯体に関
する。TECHNICAL FIELD The present invention relates to a novel TCNQ complex useful as a conductive material and the like.
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が電子を受け入れ
やすく、陽イオンと極めて安定なラジカル塩を作り、TC
NQ自身が独自に積み重なるという構造的特徴を有するこ
とに起因して高導電性を示す。The TCNQ complex is a charge-transfer complex compound known as an organic semiconductor, and its constituent component TCNQ easily accepts electrons and forms a radical salt that is extremely stable with cations.
It shows high conductivity due to the structural characteristics of NQ itself being uniquely stacked.
TCNQ錯体は、軽量、電導の異方性、溶融性、フィルム形
成性、加工及び成形の容易さ等、有機化合物のもつ特徴
的性質と金属として活かすことができる有利な点を有
し、このため、高機能導電性分子膜、非線形光学材料、
帯電防止剤、分子素子，生物素子への応用、電子機能を
もつ高秩序分子集合体の設計に、或は電解コンデンサや
電池の固体電解質等、様々な有機半導体分野に、その利
用が大いに期待されている化合物である。The TCNQ complex has the advantages that it can be utilized as a metal and the characteristic properties of organic compounds such as light weight, anisotropy of conductivity, meltability, film forming property, and ease of processing and molding. , High-performance conductive molecular film, nonlinear optical material,
There are great expectations for its application in applications to antistatic agents, molecular devices, biological devices, the design of highly ordered molecular assemblies with electronic functions, or in various organic semiconductor fields such as solid electrolytes for electrolytic capacitors and batteries. Is a compound.
TCNQ錯体に関しては、これまでに多数の含窒素複素環化
合物カチオンTCNQ錯体が合成されているが、本来TCNQ錯
体は有機化合物であり、置換基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てい
くことができるので、これによって導電体として要求さ
れる様々な性質の最適化を目的に応じてはかることが可
能なため、それら各種ニーズに対応し得る更に新たなTC
NQ錯体の開発が望まれている。Regarding the TCNQ complex, many nitrogen-containing heterocyclic compound cation TCNQ complexes have been synthesized so far, but the TCNQ complex is an organic compound by nature, and the structure and the structure of the TCNQ complex are gradually changed by changing the substituents and constituent elements. Since it is possible to change the properties, it is possible to optimize various properties required as a conductor according to the purpose.
Development of NQ complex is desired.
本発明は、上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、或いは光化
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 has been made in view of the current situation as described above, and an object thereof is to provide a novel TCNQ complex which is an organic conductive compound and can be expected to have various electrochemical or photochemical results.
本発明は、式 （但し、Ｒは炭素数１〜８のアルキル基を示す。）で表
わされるＮ−アルキル−２−フェニルピリジニウムカチ
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 及び中性TCNQ（TCNQ°）とを構成成分とするTCNQ錯体の
発明である。The present invention has the formula (Wherein R represents an alkyl group having 1 to 8 carbon atoms) and an N-alkyl-2-phenylpyridinium cation and 7,7,8,8-tetracyanoquinodimethane anion radical And a TCNQ complex containing neutral TCNQ (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、ｎは0.5≦ｎ≦1.5なる任意の数を表わす。） 本発明のTCNQ錯体に於て、ドナー部の式 で表わされるＮ−アルキル−２−フェニルピリジニウム
カチオンのアルキル基Ｒは、例えばメチル基、エチル
基、プロピル基、ブチル基、ペンチル基、ヘキシル基、
ヘプチル基、オクチル基等、炭素数１〜８のアルキル基
を示し、直鎖状のものでも分枝状のものでもよい。 (In the formula, n represents any number of 0.5 ≦ n ≦ 1.5.) In the TCNQ complex of the present invention, the formula of the donor part The alkyl group R of the N-alkyl-2-phenylpyridinium cation represented by is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
It represents an alkyl group having 1 to 8 carbon atoms such as a heptyl group and an octyl group, which may be linear or branched.
本発明のTCNQ錯体は、ヨードイオンI-の還元性を利用
し、Ｎ−アルキル−２−フェニルピリジニウムカチオン
アイオダイド と中性TCNQをモル比3:4で反応させる方法、或いは同カ
チオンのハロゲン化物とTCNQのLi塩とを反応させて を得、これに中性TCNQをドーピングさせる方法等、自体
公知の方法により容易に合成することができる。INDUSTRIAL APPLICABILITY The TCNQ complex of the present invention utilizes the reducibility of iodo ion I − to produce N-alkyl-2-phenylpyridinium cation iodide. And neutral TCNQ at a molar ratio of 3: 4, or by reacting a halide of the same cation with a Li salt of TCNQ. And can be easily synthesized by a method known per se, such as a method of doping this with neutral TCNQ.
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で電流電圧
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。ρ＝Ｒ・A/l。但し、ρは比抵抗値（Ω・cm）、
Ｒは抵抗（Ω）、Ａは電極接触面積（cm2）、ｌは試料
の厚さ（cm）である。また、熱的性質は、示差走査熱量
（DSC）測定等の熱分析で測定することができる。The synthesized TCNQ complex of the present invention can be identified by the color unique to the charge transfer complex and the appearance of the charge transfer absorption band,
The complex composition ratio can be determined from elemental analysis and ultraviolet absorption spectrum measurement. The electrical property, for example, the specific resistance value, can be obtained from the following equation by molding the sample powder into pellets, measuring the current / voltage by the two-terminal method to calculate the resistance value R. ρ = R · A / l. However, ρ is the specific resistance value (Ω · cm),
R is the resistance (Ω), A is the electrode contact area (cm 2 ), and 1 is the sample thickness (cm). The thermal property can be measured by thermal analysis such as differential scanning calorimetry (DSC) measurement.
本発明の新規なTCNQ錯体は、特にその単独又は混合品の
導電性、加工及び成形性に優れているので、これを高機
能導電性分子膜、非線形光学材料、これらの分子素子、
生物素子への応用など電子機能をもつ高秩序分子集合体
の設計に、或いは電解コンデンサや電池の固体電解質と
して等様々な有機半導体分野に於て有効に用い得ること
が期待できる。The novel TCNQ complex of the present invention is particularly excellent in conductivity, processing and moldability of a single product or a mixture product thereof, and therefore, it can be used as a highly functional conductive molecular film, a non-linear optical material, or a molecular element thereof,
It can be expected to be effectively used in various organic semiconductor fields such as the design of highly ordered molecular assemblies having electronic functions such as application to biological devices, or as a solid electrolyte of electrolytic capacitors and batteries.
以下に実施例を示すが、本発明はこれら実施例により何
等制約を受けるものではない。Examples will be shown below, but the present invention is not limited to these examples.
実施例1. （１）Ｎ−ｎ−ブチル−２−フェニルピリジニウムアイ
オダイドの合成 ２−フェニルピリジン4.7g（0.03モル）とｎ−ブチルア
イオダイド5.6gを100〜120℃で５時間加熱反応させ、反
応後、室温下、酢酸エチルで反応液を十分洗浄し、分離
した油状物を濃縮して黄色粘稠油状物7.5gを得た。（収
率73.7％） 元素分析値（C15H18NI） 計算値:C％ 53.11, H％ 5.35, N％ 4.13 実測値:C％ 52.71, H％ 5.60, N％ 4.391 HNMRδppm（CDCl3） 0.77（3H,t,J＝6Hz,Ｎ−(CH2)3 CH3 ),0.93〜1.50（2H,
m,J＝7Hz,−CH2 −）,1.50〜2.10（2H,m,J＝7Hz,−CH
2 −）,4.75（2H,t,J＝7Hz,Ｎ−CH2 -),7.61（5H,s,ベ
ンゼン環水素）7.37〜8.40（2H,m,ピリジン環C3，C5水
素）,8.79（1H,t,ピリジン環C4水素）,9.63（1H,d,ピリ
ジン環C2水素） （２）TCNQ錯体の合成 アセトニトリル150mlにTCNQ3.06g（15ミリモル）を加温
溶解し、これに（１）で得たＮ−ｎ−ブチル−２−フェ
ニルピリジニウムアイオダイド3.82gを溶解したアセト
ニトリル溶液100mlを滴下し、還流下、１時間反応させ
た。反応後冷却し、析出した結晶を取し、アセトニト
リルより再結して2.8gの黒紫色針状晶を得た。（収率6
0.1％） 元素分析値（C39H26N9） 計算値:C％ 75.47, H％ 4.22, N％ 20.31 実測値:C％ 75.33, H％ 4.26, N％ 20.41 比抵抗値:3Ω・cm DSC:吸熱点 195℃；発熱分解点 273℃。Example 1. (1) Synthesis of N-n-butyl-2-phenylpyridinium iodide 4.7 g (0.03 mol) of 2-phenylpyridine and 5.6 g of n-butyl iodide were reacted by heating at 100 to 120 ° C for 5 hours. After the reaction, the reaction solution was thoroughly washed with ethyl acetate at room temperature, and the separated oily matter was concentrated to obtain 7.5 g of a yellow viscous oily matter. (Yield 73.7%) Elemental analysis value (C 15 H 18 NI) Calculated value: C% 53.11, H% 5.35, N% 4.13 Measured value: C% 52.71, H% 5.60, N% 4.39 1 HNMRδppm (CDCl 3 ) 0.77 (3H, t, J = 6Hz, N- (CH 2) 3 CH 3), 0.93~1.50 (2H,
m, J = 7Hz, −CH 2 −), 1.50 to 2.10 (2H, m, J = 7Hz, −CH
2 -), 4.75 (2H, t, J = 7Hz, N- CH 2 -), 7.61 (5H, s, benzene ring hydrogen) 7.37-8.40 (2H, m, pyridine ring C 3, C 5 hydrogen), 8.79 (1H, t, pyridine ring C 4 hydrogen), 9.63 (1H, d, pyridine ring C 2 hydrogen) (2) Synthesis of TCNQ complex TCNQ 3.06g (15 mmol) was dissolved in 150 ml of acetonitrile under heating, and ( 100 ml of an acetonitrile solution in which 3.82 g of Nn-butyl-2-phenylpyridinium iodide obtained in 1) was dissolved was added dropwise, and the mixture was reacted under reflux for 1 hour. After the reaction, the mixture was cooled and the precipitated crystals were collected and recrystallized from acetonitrile to obtain 2.8 g of black purple needle crystals. (Yield 6
0.1%) Elemental analysis value (C 39 H 26 N 9 ) Calculated value: C% 75.47, H% 4.22, N% 20.31 Actual value: C% 75.33, H% 4.26, N% 20.41 Specific resistance value: 3Ω ・ cm DSC : Endothermic point 195 ° C; exothermic decomposition point 273 ° C.
尚、中性TCNQ（TCNQ°と表示）とアニオンラジカルTCNQ との錯体構成比 は文献（A.Rembaum etc.,J.Am.Chem.Soc.,93,2532（197
1））に従い紫外線吸収スペクトル測定方法で求めた。
又、吸熱点及び発熱分解点については示差走査熱量（DS
C）測定で求めた。電気的特性値については錯体をペレ
ットとし、以下常法に従って試料作製の後25℃で電流電
圧測定（二端子法）を行ない、前記計算式に基づいて比
抵抗値ρ（Ω・cm）を求めた。 In addition, neutral TCNQ (displayed as TCNQ °) and anion radical TCNQ Complex composition ratio with (A. Rembaum etc., J. Am. Chem. Soc., 93 , 2532 (197
It was determined by the method of ultraviolet absorption spectrum measurement according to 1)).
The differential scanning calorific value (DS
C) Obtained by measurement. Regarding the electrical characteristic values, the complex was made into pellets, and the current-voltage measurement (two-terminal method) was performed at 25 ° C after sample preparation according to the usual method below, and the specific resistance value ρ (Ωcm) was calculated based on the above calculation formula. It was
以上述べた如く、本発明は、これまでTCNQ錯体に用いら
れていなかったＮ−アルキル−２−フェニルピリジニウ
ムカチオンをドナーとして用いた点に特徴を有する発明
であり、従来にない種々の電子化学的或いは光学的成果
が期待できる新規な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 by the use of an N-alkyl-2-phenylpyridinium cation, which has not been used in TCNQ complexes, as a donor. Alternatively, it has a remarkable effect in that it can provide a novel TCNQ complex that can be expected to have optical results, and is a great invention that contributes to the industry.
Claims (1)
わされるＮ−アルキル−２−フェニルピリジニウムカチ
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 及び中性TCNQ（TCNQ°）とを構成成分とするTCNQ錯体。1. A formula (Wherein R represents an alkyl group having 1 to 8 carbon atoms) and an N-alkyl-2-phenylpyridinium cation and 7,7,8,8-tetracyanoquinodimethane anion radical And a TCNQ complex containing neutral TCNQ (TCNQ °) as a constituent component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15949586A JPH0684352B2 (en) | 1986-07-07 | 1986-07-07 | Novel TCNQ complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15949586A JPH0684352B2 (en) | 1986-07-07 | 1986-07-07 | Novel TCNQ complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6314769A JPS6314769A (en) | 1988-01-21 |
| JPH0684352B2 true JPH0684352B2 (en) | 1994-10-26 |
Family
ID=15695016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15949586A Expired - Lifetime JPH0684352B2 (en) | 1986-07-07 | 1986-07-07 | Novel TCNQ complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0684352B2 (en) |
-
1986
- 1986-07-07 JP JP15949586A patent/JPH0684352B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6314769A (en) | 1988-01-21 |
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