JPS62230796A - Bis(dithiolene)metal complex compound - Google Patents
Bis(dithiolene)metal complex compoundInfo
- Publication number
- JPS62230796A JPS62230796A JP7326286A JP7326286A JPS62230796A JP S62230796 A JPS62230796 A JP S62230796A JP 7326286 A JP7326286 A JP 7326286A JP 7326286 A JP7326286 A JP 7326286A JP S62230796 A JPS62230796 A JP S62230796A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- bis
- liquid crystal
- compound
- complex compound
- 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.)
- Pending
Links
- -1 metal complex compound Chemical class 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 8
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 abstract description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 6
- 150000004795 grignard reagents Chemical class 0.000 abstract description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 abstract description 4
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007818 Grignard reagent Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical group Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- YCBFZJMOWMCVHZ-UHFFFAOYSA-N C=1C=CC=CC=1C(P(=O)=O)(C)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C(P(=O)=O)(C)C1=CC=CC=C1 YCBFZJMOWMCVHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 14
- 239000004020 conductor Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000018 DNA microarray Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000004768 bromobenzenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 description 1
- IKPSIIAXIDAQLG-UHFFFAOYSA-N 1-bromoundecane Chemical compound CCCCCCCCCCCBr IKPSIIAXIDAQLG-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 101100229939 Mus musculus Gpsm1 gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XIUROWKZWPIAIB-UHFFFAOYSA-N sulfotep Chemical compound CCOP(=S)(OCC)OP(=S)(OCC)OCC XIUROWKZWPIAIB-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は新規なビス（ジチオレン）金属錯津化合物およ
びそれらを含有するディスコティック液晶相を取り得る
組成物に間する。この物質は高い電子受容性を有するも
のとして既存のディスコティック液晶相を取り得る化合
物にない特徴を持っている。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to novel bis(dithiolene) metal complex compounds and compositions containing them which can assume a discotic liquid crystal phase. This substance has high electron-accepting properties, which is a characteristic not found in existing compounds that can form a discotic liquid crystal phase.
これらによって作ることのできる一次元導電性物質は、
その導電異方性のために各種の電子デバイスに用いられ
つるばかりでなく、分子レベルの大きさの電線としてバ
イオチップスや分子素子を構成する要素として必要不可
欠なものである。One-dimensional conductive materials that can be made using these materials are:
Due to its conductive anisotropy, it is not only used as a wire in various electronic devices, but also as an indispensable component of biochips and molecular devices as a molecular-sized electric wire.
［従来の技術］
一次元有機導電性物質としては、有名なＴＴＦ−ＴＣＮ
Ｑ錯体のように積み重なったカラム構造を形成するもの
が広く知られている。[Prior art] As a one-dimensional organic conductive material, TTF-TCN is famous.
Those that form a stacked column structure like the Q complex are widely known.
ディスコティック液晶は、これら−次元有機導電性物質
と同様に積み重なったカラム構造を形成するが、一般に
は電子の授受はおこなわない、しかしディスコティック
液晶で電子供与性を有するものは知られており（Ｃ，Ｐ
ｉｅｃｈｏｃｋｉ ｅｔ、ａｌ、、 ＪＡＣ８」ＪＡ、
５２４５； Ｒ，Ｆｕｇｎｉｔｔｏ ｅｔ、ａｌ、
、Ｊ、Ｃ，Ｓ、Ｃｈｅｍ、Ｃｏｍｍ、、（１９８０）２
７１； Ｊ、Ｃ，Ｄｕｂｏｉｓ、Ａｎｎ、Ｐｈｙｓ、
、３，１３１（１９７８）； Ａ、Ｂｅｇｉｎ ｅ
ｔ、ａｌ、、Ｊ、ｄｅ Ｐｈｙｓｉｑｕｅ、４０．Ｃ
５−１５（１９７９）） 、ＢＦ４ 、 Ｃ１０ａ 、
ＴＣＮＱなとの電子受容体と組み合わせてＣＴ錯体が
作られ、これによって−次元導電体が得られている。Discotic liquid crystals form a stacked column structure similar to these two-dimensional organic conductive materials, but they generally do not give or receive electrons; however, some discotic liquid crystals that have electron-donating properties are known ( C,P
iechocki et, al,, JAC8” JA,
5245; R, Fugnitto et al.
, J.C.S., Chem., Comm., (1980) 2
71; J.C. Dubois, Ann, Phys.
, 3, 131 (1978); A. Begin e.
t,al,,J,de Physique,40. C
5-15 (1979)), BF4, C10a,
In combination with an electron acceptor such as TCNQ, a CT complex has been created, resulting in a -dimensional conductor.
［発明が解決しようとする問題点］
しかし、従来の通常の一次元的有機導電性物質は、分子
が積み重なったカラムの長さをあまり長くできないため
に導電性が低く、導電性を高くするためには各々のカラ
ム間を接続するための極端に多い量のドーピング剤など
を必要とした。これらのドーピング剤は毒性の高いもの
がほとんどで、製造において危険なばかりでなく脱ドー
プによって導電性の低下や周囲を汚染する危険を絶えず
はらんでいるという問題点があった。さらにドーピング
によって、電気伝導率の異方性も低くなってしまう欠点
があった。[Problems to be solved by the invention] However, conventional one-dimensional organic conductive materials have low conductivity because the length of the column in which molecules are stacked cannot be made very long. This required an extremely large amount of doping agent to connect each column. Most of these doping agents are highly toxic, and are not only dangerous during production, but also have the problem of constantly running the risk of reducing conductivity and contaminating the surrounding area due to dedoping. Furthermore, doping has the disadvantage that the anisotropy of electrical conductivity also decreases.
また、ディスコティック）成品は長いカラム状の構造を
取るが、はとんどのものは電気的に良い絶縁体である。Also, discotic products have a long column-like structure, but most of them are good electrical insulators.
さらに、先に述べた電子供与性のディスコティック液晶
単独では導電性とはならず、通常の電子受容体との混合
によるＣ Ｔ ｇｒｉ体などを作って導電性としている
が、この電子受容体は非液晶のために混合物全体の液晶
性が低下して、液晶相をとる温度範囲が狭くなったり、
カラムの形成を妨げて電気伝導性や導電異方性を下げる
などの欠点があった。Furthermore, the electron-donating discotic liquid crystal mentioned above alone is not conductive; it is made to be conductive by mixing it with a normal electron acceptor to form a C T gri body, but this electron acceptor is Because it is non-liquid crystal, the liquid crystallinity of the entire mixture decreases, and the temperature range in which it takes on a liquid crystal phase becomes narrower.
It has drawbacks such as hindering the formation of columns and lowering electrical conductivity and conductive anisotropy.
そこで本発明は、電子受容性のディスコティック液晶に
よって、以上述べたような通常の一次元的有機導電性物
質や、ディスコティック液晶と液晶以外の電子受容体と
の混合によるＣ Ｔ ｔａ体などによる、−次元導電体
の欠点を解決するためになされたものであり、ディスコ
ティック液晶同士によるＣＴ錯体形成によって電子を運
ぶカラムの長さを長くし、電気伝導性と導電異方性の高
い一次元導電性物質を構成し得る、電子受容性の有機金
ｆｆ１ｆａ体化合物を供与することを目的するものであ
る。Therefore, the present invention utilizes an electron-accepting discotic liquid crystal, an ordinary one-dimensional organic conductive substance as described above, or a C T ta body formed by mixing a discotic liquid crystal with an electron acceptor other than a liquid crystal. This was developed to solve the drawbacks of -dimensional conductors, and the length of the column carrying electrons is lengthened by CT complex formation between discotic liquid crystals, resulting in one-dimensional conductors with high electrical conductivity and conductive anisotropy. The object of the present invention is to provide an electron-accepting organic gold ff1fa compound that can constitute a conductive substance.
［問題点を解決するための手段］
本発明者らは、金属錯体、ディスコティック液晶につい
てその骨格を含め鋭意検討を重だ結果、下記一般式［■
］で表わされるビス（ジチオレン）金属錯体化合物が、
高い電子受容性およびディスコティック液晶相を呈する
ことにより、高い電気伝導性と導電異方性を持つディス
コティック液晶相を取り得る物質となりうることを見い
出した。[Means for Solving the Problems] The present inventors have conducted intensive studies on metal complexes and discotic liquid crystals, including their skeletons, and have developed the following general formula [■
] A bis(dithiolene) metal complex compound represented by
We have discovered that by exhibiting high electron acceptability and a discotic liquid crystal phase, it can be a material that can take a discotic liquid crystal phase with high electrical conductivity and conductive anisotropy.
［式中、Ｒは脂肪属アルキルもしくはアルコキシ基を表
わし、Ｍは中心金属を表わす、］［１１式の化合物は、
例えば以下の手順によって合成できる。[In the formula, R represents an aliphatic alkyl or alkoxy group, and M represents a central metal.] [The compound of formula 11 is
For example, it can be synthesized by the following procedure.
ｓ ｃ ｈ ｅ ｍ ｅ １以下その
概略を説明する。s ch e me 1 The outline will be explained below.
ｐ−ブロモフェノールをブロモアルカン、アルキルスル
ホン酸エステル等を用いて、常法によりエーテル化せし
め得られるｐ−アルコキシブロモベンゼン、もしくはア
ルキルベンゼンをブロム化して得たアルキルブロモベン
ゼン。p-alkoxybromobenzene obtained by etherifying p-bromophenol using a bromoalkane, alkylsulfonic acid ester, etc. by a conventional method, or alkylbromobenzene obtained by brominating an alkylbenzene.
これらのＰ−置換ブロモベンゼン［ＩＩ］をグリニヤー
ル試薬［ＩＩＩ ］ として、塩化ニッケルのジフェニ
ル７オスフオエタン錯体存在下にトランス１゜２−ジク
ロロエチレンを反応せしめることでスチルベン誘導体［
ＩＹ ］が得られる。これを二酸化セレン等を用いて酸
化することにより、ベンジル誘導体［Ｖ］が得られる。These P-substituted bromobenzenes [II] were used as Grignard reagents [III] to react with trans-1°2-dichloroethylene in the presence of a diphenyl-7-osphoethane complex of nickel chloride to obtain stilbene derivatives [III].
IY ] is obtained. By oxidizing this using selenium dioxide or the like, benzyl derivative [V] is obtained.
これにまず五疏化リン、次いで例えば塩化ニッケルのよ
うな金属塩等を反応せしめれば、関わるビス（ジチオレ
ン）金属錯体化合物が得られる。If this is first reacted with phosphorus pentahydride and then with a metal salt such as nickel chloride, the related bis(dithiolene) metal complex compound can be obtained.
式［１］の化合物において、Ｒは炭素数１〜１５の脂肪
属アルキルもしくはアルコキシを示すが、液晶性あるい
はカラム形成能等を考慮すると、Ｒは特に炭素数５〜１
２の脂肪属アルキルもしくはアルコキシである化合物が
好ましい。In the compound of formula [1], R represents aliphatic alkyl or alkoxy having 1 to 15 carbon atoms, but in consideration of liquid crystallinity or column forming ability, R is particularly alkyl having 5 to 1 carbon atoms.
Compounds which are fatty alkyl or alkoxy of 2 are preferred.
また、式［＋１の化合物は６０〜２００°Ｃ以上の広い
温度領域においてディスコティック液晶相を呈する。さ
らにこれらの適切な混合によりその温度範囲は各種電子
デバイス等の実用温度領域を含みかなり広く制御できる
。Further, the compound of formula [+1 exhibits a discotic liquid crystal phase in a wide temperature range of 60 to 200°C or higher. Furthermore, by appropriately mixing these, the temperature range can be controlled over a fairly wide range, including the practical temperature range of various electronic devices.
以下、実施例として物質の製造を例示し本発明の態様を
詳しく述べる。Hereinafter, embodiments of the present invention will be described in detail by illustrating the production of substances as examples.
［実施５ｆＩ １ ］
ビス［１，２−ジ（ｐ−ｎ−ノニロキシフェニル）エチ
レン−１，２−ジチオン］ニッケルの製造
エタノール１０１００Ｏにｐ−ブロモフェノール１ｍｏ
１を溶かし、ＫＯ）（１，１ｍｏｌを加えてから１−ブ
ロモノナン１．０５ｍｏｌを加えて加熱還流した。得ら
れた生成物を分離した後、１５０ｇとってＴ ＨＦ ５
００ ｍ ｌ中でマグネシウム１２ｇを加えグリニヤー
ル試薬を調製し１次いでトランス１，２−ジクロロエチ
レン３１ｇを加え、塩化ニッケルのジフェニルフォスフ
オニタン錯体を加え加熱還流した。得られたスチルベン
誘導体（５２％ｙｉｅｌｄ）を分離して、そのうち９３
ｇを９０％ＡｃＯＨ中で触媒量の硫酸を加えて二酸化セ
レンによって酸化させ、ベンジル誘導体を得た（３４％
ｙｉｅｌｄ）、このベンジル誘導体のうち３０ｇを五疏
化リンで１．２−ジ（ｐ−ｎ−）二口キシフェニル）エ
チレン−１，２−ジチオンにした後、塩化ニッケルを加
えて錯体を作り、目的とするビス［１，２−ジ（ｐ−ｎ
−ノニロキシフェニル）エチレン−１，２−ジチオン］
ニッケルを得たく３０％ｙｉｅｌｄ）。[Execution 5fI 1] Production of bis[1,2-di(p-n-nonyloxyphenyl)ethylene-1,2-dithione]nickel 1 mo of p-bromophenol in 10100 O of ethanol
1 was dissolved, KO) (1,1 mol was added thereto, 1.05 mol of 1-bromononane was added, and the mixture was heated to reflux. After separating the obtained product, 150 g was taken and dissolved in THF 5
A Grignard reagent was prepared by adding 12 g of magnesium in 0.00 ml, and then 31 g of trans-1,2-dichloroethylene was added, followed by a diphenylphosphonitane complex of nickel chloride, and the mixture was heated to reflux. The obtained stilbene derivative (52% yield) was separated, and 93
g was oxidized with selenium dioxide in 90% AcOH with catalytic amount of sulfuric acid to give the benzyl derivative (34%
yield), 30g of this benzyl derivative was converted into 1,2-di(p-n-)dioxyphenyl)ethylene-1,2-dithione with phosphorus pentacaride, and then nickel chloride was added to form a complex. Target bis[1,2-di(p-n
-nonyloxyphenyl)ethylene-1,2-dithione]
30% yield to obtain nickel).
元素分析の結果、水素８．３５％（計算値８゜３４％）
、炭素６９．３７％（計ｎ値６９．１０％）となり、計
算値との一致をみた。As a result of elemental analysis, hydrogen 8.35% (calculated value 8°34%)
, carbon was 69.37% (total n value 69.10%), which was consistent with the calculated value.
赤外吸光分析の結果、第１図に示すように２８５０、２
９１０ｃｍ−１にアルキル基、１０４０，１５００．１
６００ｃｍ−１に芳香環、１２５０ｃｍ−１にアリール
アルキルエーテル、１２９０．１３４０ｃｍ （にチオ
ンに由来する吸収が観察された。As a result of infrared absorption analysis, as shown in Figure 1, 2850,2
Alkyl group at 910 cm-1, 1040, 1500.1
Absorption derived from an aromatic ring at 600 cm-1, an arylalkyl ether at 1250 cm-1, and a thione at 1290.1340 cm was observed.
プロトンＮＭＲではδ７．０に芳香環による四１線、６
３．９に（−０−ＣＨｄｓ）＋、１ｍよる三重線、６１
．４にメチレンによる多重線、δ０．９にメチルによる
三重線が観察された。In proton NMR, there is a 41 line due to aromatic ring at δ7.0, 6
3.9 (-0-CHds)+, triple line by 1m, 61
．． A multiplet due to methylene was observed at 4, and a triplet due to methyl was observed at δ0.9.
このものは低温結晶に１ （融点１０９°Ｃ）と高温結
晶に２ （融点１３０°Ｃ）とを有し、酢酸エチル溶
媒からの再結晶により得られるのはＫ ２であった。各
々の結晶相を昇温するとディスコティック液晶相を取り
、さらに昇温すると等方性液体となった、各転移温度お
よびエンタルピー変化を表１に示す。This had a low temperature crystal of 1 (melting point 109°C) and a high temperature crystal of 2 (melting point 130°C), and K 2 was obtained by recrystallization from ethyl acetate solvent. Table 1 shows the transition temperature and enthalpy change of each crystal phase, which takes on a discotic liquid crystal phase when the temperature is increased, and becomes an isotropic liquid when the temperature is further increased.
サイクリックポルタモメトリーによって測定したところ
半波電位は一〇、０６Ｖとなり、電子受容性を示した。When measured by cyclic portamometry, the half-wave potential was 10.06 V, indicating electron acceptability.
［実施例２］
ビス［１，２−ジ（ｐ −＋１−ウンデシロキシフェニ
ル）エチレン−１，２−ジチオン］ニッケルの製造
実施例１と同様にして、エタノール１０００ ｍｌにｐ
−ブロモフェノール１ ｍ ｏ １を溶かし、Ｋ○Ｈ１
，１ｍｏｌを加えてから１−ブロモウンデカン１．０５
ｍｏｌを加えて加熱還流した。得られた生成物を分離し
、１６４ｇ取ってＴＨＦ５００ｍｌ中でマグネシウム１
２ｇを加えグリニアール試薬を調製し、次いでトランス
１．２−ジクロロエチレン３１ｇを加え、塩化ニッケル
のジフェニルフォスフオニタン錯体を加え加熱還流した
。[Example 2] Production of bis[1,2-di(p −+1-undecyloxyphenyl)ethylene-1,2-dithione]nickel In the same manner as in Example 1, p was added to 1000 ml of ethanol.
-Dissolve 1 m o 1 of bromophenol, K○H1
, 1 mol and then 1-bromoundecane 1.05
mol was added and heated to reflux. The obtained product was separated, 164 g was taken, and 1 magnesium was added in 500 ml of THF.
2 g was added to prepare a Grignard reagent, then 31 g of trans-1,2-dichloroethylene was added, and a diphenylphosphonitane complex of nickel chloride was added, followed by heating under reflux.
得られたスチルベン誘導体（６５％ｙｉｅｌｄ）を分離
して、そのうち９８．５ｇを９０％ＡｃＯＨ中で触媒量
の硫酸を加えて二酸化セレンによって酸化させ、ベンジ
ル誘導体を得た（２９％ｙｉｅ ｌ ｄ ） ｅこのベ
ンジル誘導体のうち２５ｇを五疏化リンで１．２−ジ（
ｐ−ｎ−ウンデシロキシフェニル）エチレン−１，２−
ジチオンにした後、塩化ニッケルを加えて錯体を作り、
目的とするビス［１，２−ジ（ｐ−ｎ−ウンデシロキシ
フェニル）エチレン−１，２−ジチオン］ニッケルを得
た（３１％ｙｉｅｌｄ）。The obtained stilbene derivative (65% yield) was separated and 98.5 g of it was oxidized with selenium dioxide in 90% AcOH with the addition of a catalytic amount of sulfuric acid to obtain the benzyl derivative (29% yield). e 25g of this benzyl derivative was dissolved in 1,2-di(
p-n-undecyloxyphenyl)ethylene-1,2-
After converting it into dithion, add nickel chloride to make a complex,
The target bis[1,2-di(p-n-undecyloxyphenyl)ethylene-1,2-dithione]nickel was obtained (31% yield).
このものも実施例１と同様に低温結晶Ｋ 、と高温結晶
Ｋ ２とを有し、酢酸エチル溶媒からの再結晶により得
られるのはに２であった。各々の結晶相を昇温するとデ
ィスコティック液晶相を取り、さらに昇温すると等方性
液体となった。各転移温度およびエンタルピー変化を表
１に示す。This product also had low-temperature crystals K 2 and high-temperature crystals K 2 as in Example 1, and only 2 was obtained by recrystallization from an ethyl acetate solvent. When each crystal phase was heated, a discotic liquid crystal phase was obtained, and when the temperature was further increased, it became an isotropic liquid. Table 1 shows each transition temperature and enthalpy change.
サイクリックポルタモメトリーによって測定したところ
半波電位は−０，０７Ｖとなり、電子受容性を示した。When measured by cyclic portamometry, the half-wave potential was -0.07 V, indicating electron acceptability.
元素分析の結果、水素８．８７％（計算値８゜８９％）
、炭素７０．７２％（計算値７０．６２％）となり計算
値との一致をみた。As a result of elemental analysis, hydrogen 8.87% (calculated value 8°89%)
, carbon was 70.72% (calculated value 70.62%), which was consistent with the calculated value.
赤外吸光分析およびプロトンＮＭＲによるスペクトルは
実施例１と同様のものが得られた。The same spectra as in Example 1 were obtained by infrared absorption analysis and proton NMR.
Ｋ ＝ １３晶相、Ｄ＝ニブイスコテイック晶相。K = 13 crystal phase, D = nibiscotic crystal phase.
１、Ｌ、＝等方性液体相
［実施例３］
他のビス［１，２−ジ（ｐ−ｎ−アルコキシフェニル）
エチレン−１，２−ジチオン］ニッケル錯体化合物の合
成
実施例１．２と同様にして式［１１のアルコキシ基の炭
素数１．２，３，４，５，６，７，８゜１０．１２のニ
ッケル錯体も合成した。1,L,=isotropic liquid phase [Example 3] Other bis[1,2-di(p-n-alkoxyphenyl)
Synthesis of ethylene-1,2-dithione]nickel complex compound In the same manner as in Example 1.2, carbon number of alkoxy group of formula [11: 1.2, 3, 4, 5, 6, 7, 8° 10.12 A nickel complex was also synthesized.
これらは炭素数７〜１２でディスコティック液晶相をし
めした。これらのものと実施例１．２のものの、融点（
ｍ、ｐ） 、等方点（ｃ、ｐ）と元素分析の結果をまと
めて表２に示す。These had 7 to 12 carbon atoms and exhibited a discotic liquid crystal phase. The melting points (
m, p), isotropic points (c, p), and the results of elemental analysis are summarized in Table 2.
表２
［実施例４］
上記実施例１と２で得られた化合物を任意に混合し、混
合系の遷移点の変化を調べた。結果を第２図に示す０図
よりわかるように理想的な共晶カーブを措き、適切な配
合により広い温度範囲を有する液晶組成物が構成できる
。Table 2 [Example 4] The compounds obtained in Examples 1 and 2 above were arbitrarily mixed, and changes in the transition point of the mixed system were investigated. As can be seen from the results shown in Figure 2, a liquid crystal composition having a wide temperature range can be constructed by excluding the ideal eutectic curve and by appropriately blending the compositions.
［発明の効果］
以上述べたように、本発明によれば新しい電子受容性の
ディスコティック液晶相を取る物質を得ることができる
。これと電子供与性のディスコティック液晶との組み合
わせで得られる導電体は、１夜晶であるために配向制御
が容易であり、カラムの形成がうまくいくためにドーピ
ング剤が無いがまたは掻く少量ですみ、積み重なったカ
ラム構造を取るために導電異方性にすぐれた一次元性の
有機導電体となる。これらの−次元性の有機導電体は各
種の電子デバイスに用いられうるばがりでなく、分子レ
ベルの大きさの電線としてバイオチップスや分子素子を
構成する要素等として極めて有用なものである。[Effects of the Invention] As described above, according to the present invention, a new electron-accepting substance exhibiting a discotic liquid crystal phase can be obtained. The conductor obtained by combining this with an electron-donating discotic liquid crystal is an overnight crystal, which makes it easy to control the orientation, and requires no doping agent or a small amount of doping agent to ensure successful column formation. Because it has a stacked column structure, it becomes a one-dimensional organic conductor with excellent conductive anisotropy. These one-dimensional organic conductors can not only be used in various electronic devices, but also extremely useful as molecular-level electric wires, elements constituting biochips and molecular devices, and the like.
第１図は、実施例１で合成したビス［１，２−９（ｐ−
ｎ−／ワキキシフェニル）エチレ７−１゜２−ジチオン
］ニッケルの赤外吸収スペクトル図である。
第２図はビス［１，２−ジ（ｐ−ｎ−〕二ワキシフェニ
ル）エチレン−１，２−ジチオン］ニッケルル（実施例
１の化合物）とビス［１，２−ジ（ｐ−ｎ−’ｙンデシ
ロキシフェニル）エチレン−１，２−ジチオン］ニッケ
ル（実施例２の化合物）の混合系の遷移点の変化図（共
晶カーブ）を示す。
以上Figure 1 shows bis[1,2-9(p-
FIG. 2 is an infrared absorption spectrum diagram of n-/waxyphenyl)ethyle 7-1°2-dithione]nickel. Figure 2 shows bis[1,2-di(p-n-]diwaxyphenyl)ethylene-1,2-dithione]nickelyl (compound of Example 1) and bis[1,2-di(p-n-' FIG. 2 shows a change diagram (eutectic curve) of the transition point of a mixed system of y-indecyloxyphenyl)ethylene-1,2-dithione]nickel (compound of Example 2). that's all
Claims (4)
アルコキシ基を表わし、Ｍは中心金属を表わす。］(1) A metal complex compound having the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R represents an aliphatic alkyl or alkoxy group having 1 to 15 carbon atoms, and M represents a central metal. ]
であることを特徴とするビス（ジチオレン）金属錯体化
合物。(2) In claim (1), the central metal is Ni
A bis(dithiolene) metal complex compound characterized by:
アルコキシ基を表わし、Ｍは中心金属を表わす。］で表
わされるビス（ジチオレン）金属錯体化合物を、少なく
とも１種類含有することを特徴とするディスコアイック
液晶相を取り得る組成物。(3) General formula ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [I] [In the formula, R represents an aliphatic alkyl or alkoxy group having 1 to 15 carbon atoms, and M represents a central metal. ] A composition capable of taking a discoaic liquid crystal phase, characterized by containing at least one type of bis(dithiolene) metal complex compound represented by the following.
であるビス（ジチオレン）金属錯体化合物を、少なくと
も１種類含有することを特徴とするディスコアイック液
晶相を取り得る組成物。(4) In claim (3), the central metal is Ni
1. A composition capable of taking a discoaic liquid crystal phase, characterized in that it contains at least one type of bis(dithiolene) metal complex compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7326286A JPS62230796A (en) | 1986-03-31 | 1986-03-31 | Bis(dithiolene)metal complex compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7326286A JPS62230796A (en) | 1986-03-31 | 1986-03-31 | Bis(dithiolene)metal complex compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62230796A true JPS62230796A (en) | 1987-10-09 |
Family
ID=13513085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7326286A Pending JPS62230796A (en) | 1986-03-31 | 1986-03-31 | Bis(dithiolene)metal complex compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230796A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010006766A (en) * | 2008-06-27 | 2010-01-14 | Nippon Oil Corp | New organometal complex compound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58209594A (en) * | 1982-05-31 | 1983-12-06 | Nippon Telegr & Teleph Corp <Ntt> | Optical recording medium |
| JPS592880A (en) * | 1982-06-30 | 1984-01-09 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of optical recording thin-film medium |
| JPS6180106A (en) * | 1984-09-27 | 1986-04-23 | Fuji Photo Film Co Ltd | Infrared absorption composition |
| JPS61225192A (en) * | 1985-02-20 | 1986-10-06 | バスフ アクチェン ゲゼルシャフト | Novel tetraphenyldithiol complex and use |
-
1986
- 1986-03-31 JP JP7326286A patent/JPS62230796A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58209594A (en) * | 1982-05-31 | 1983-12-06 | Nippon Telegr & Teleph Corp <Ntt> | Optical recording medium |
| JPS592880A (en) * | 1982-06-30 | 1984-01-09 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of optical recording thin-film medium |
| JPS6180106A (en) * | 1984-09-27 | 1986-04-23 | Fuji Photo Film Co Ltd | Infrared absorption composition |
| JPS61225192A (en) * | 1985-02-20 | 1986-10-06 | バスフ アクチェン ゲゼルシャフト | Novel tetraphenyldithiol complex and use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010006766A (en) * | 2008-06-27 | 2010-01-14 | Nippon Oil Corp | New organometal complex compound |
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