JPH01106022A - Organic nonlinear optical material and production thereof - Google Patents
Organic nonlinear optical material and production thereofInfo
- Publication number
- JPH01106022A JPH01106022A JP62264526A JP26452687A JPH01106022A JP H01106022 A JPH01106022 A JP H01106022A JP 62264526 A JP62264526 A JP 62264526A JP 26452687 A JP26452687 A JP 26452687A JP H01106022 A JPH01106022 A JP H01106022A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- gel
- optical material
- organic nonlinear
- formula
- 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
- 230000003287 optical effect Effects 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- -1 halogen ion Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 20
- 238000005342 ion exchange Methods 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 6
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 229920000547 conjugated polymer Polymers 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical class C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YOBTXORLVXZWSR-UHFFFAOYSA-M 1,4-dimethylpyridin-1-ium;iodide Chemical compound [I-].CC1=CC=[N+](C)C=C1 YOBTXORLVXZWSR-UHFFFAOYSA-M 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- UDCDOJQOXWCCSD-UHFFFAOYSA-N N,N-dimethyl-N'-p-tolylsulfamide Chemical compound CN(C)S(=O)(=O)NC1=CC=C(C)C=C1 UDCDOJQOXWCCSD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Pyridine Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の産業上利用分野）
本発明は有機非線形光学材料およびその製造方法、さら
に詳細には、光双安定素子などの非線形光学素子用素材
として有用な有機非線形光学材料およびそのＩｎ方法に
関するものである。Detailed Description of the Invention (Industrial Application Field of the Invention) The present invention relates to an organic nonlinear optical material and a method for producing the same, and more particularly, to an organic nonlinear optical material useful as a material for a nonlinear optical element such as an optical bistable element. and its In method.
〔発明の従来技術および問題点］
三次の非線形光学材料は、光双安定現象を利用した光ス
インチ、光メモリへの応用が可能であるため、将来の光
素子の中心素材として、活発な研究開発が進められてい
る。中でも有機非線形光学材料は、■ＫＤＰ・ＬｉＮｂ
０．などの無機強銹電体結晶に比べ、非線形光学定数が
大きい、■ガリウムー砒素などの無機゛１１導体に比べ
応答速慶が速い、■高速応答・室温動作が確認され”ζ
いる塩化第一銅（ＣｕＣｆｆｉ）では困難なμｍオーダ
ーの薄膜化が容易なこと、など従来の材料では同時に満
たされることのなかった要求条件をすべて満足する可能
性を秘めており、活発な材料探索が進められている。[Prior Art and Problems of the Invention] Third-order nonlinear optical materials can be applied to optical switches and optical memories that utilize the optical bistability phenomenon, and therefore active research and development is being conducted as core materials for future optical devices. It is progressing. Among the organic nonlinear optical materials, ■KDP/LiNb
0. It has a larger nonlinear optical constant than inorganic strong electric crystals such as gallium-arsenic, ■ has faster response speed than inorganic 11 conductors such as gallium-arsenic, and has been confirmed to have high-speed response and room temperature operation.
It has the potential to satisfy all the requirements that could not be met simultaneously with conventional materials, such as the ability to easily form thin films on the μm order, which is difficult to do with cuprous chloride (CuCffi), which is difficult to achieve with cuprous chloride (CuCffi). is in progress.
現在、三次の効果の大きい有機非線形光学材料として知
られているものは、ポリジアセチレン（特にＰＴＳ）
・ポリアセチレンに代表されるπ共役高分子がほとんど
である。しかし、これらπ共役高分子系の光非線形性は
、価電子帯の自由電子の分極を根源としているため、無
機半導体と掘めて類似した欠点、すなわち狭いバンドギ
ャップに基づいた共鳴効果による応答速度の低下から逃
れられない。Currently, polydiacetylene (especially PTS) is known as an organic nonlinear optical material with a large third-order effect.
・Most of them are π-conjugated polymers represented by polyacetylene. However, since the optical nonlinearity of these π-conjugated polymer systems is rooted in the polarization of free electrons in the valence band, they suffer from a drawback similar to that of inorganic semiconductors, namely, the response speed due to the resonance effect based on the narrow band gap. cannot escape from the decline.
一方、低分子化合物系では、ＤＥＡＮＳ ： Ｎ。On the other hand, for low-molecular compound systems, DEANS: N.
Ｎ−ジエチル−４”−二ト１コスチルベン（小林、眼部
、インターナショナル・カンタｌトエレクトロニクス・
コンファレンス・テクニカル・ダイジェスト、９０ペー
ジ、ＴＵＮＮ２、（１９８７））や、ＤＭＳ−ＰＴＳ：
Ｎ、Ｎ−ジメチル−４−アミノ−Ｎ゛−メチル−４゛−
スチルバゾリウム−Ｐ−）ルエンスルホナート（検印、
中西、開田、加藤、第４回オプティックスとエレクトロ
ニクス有機材料に関するシンポジウム講演予稿集、９−
１１、（１９８７））が、第三高調波発生効率において
π共役高分子に匹敵する特性を有していることが明らか
にされつつある。しかし、これら低分子化合物は、結晶
化のため長時間融液状態に保つと分解するなどの理由か
ら、光学純度の高い結晶材料を得ることが難しく素子応
用には至っていない。さらに、既知のスチルバゾリウム
系化合物は吸湿性が高いため、現状のままでは実用に供
すことは難しい。N-diethyl-4”-dito-1-costilbene (Kobayashi, Ophthalmology, International Kantal Electronics)
Conference Technical Digest, page 90, TUNN2, (1987)) and DMS-PTS:
N,N-dimethyl-4-amino-N゛-methyl-4゛-
Stilbazolium-P-) luenesulfonate (inspection seal,
Nakanishi, Kaida, Kato, Proceedings of the 4th Symposium on Organic Materials for Optics and Electronics, 9-
11, (1987)) has a property comparable to that of π-conjugated polymers in terms of third harmonic generation efficiency. However, these low-molecular compounds are difficult to obtain crystalline materials with high optical purity because they decompose when kept in a melt state for a long time due to crystallization, and have not been applied to devices. Furthermore, known stilbazolium compounds have high hygroscopicity, so it is difficult to put them into practical use as is.
本発明は上記問題点に鑑みなされたものであって、化学
的・物理的に安定であり、かつ高速・高効率の光非線形
応答を示す有機非線形光学材料を提供し、さらにその新
規な製造方法を提供することを目的としている。The present invention has been made in view of the above problems, and provides an organic nonlinear optical material that is chemically and physically stable and exhibits a fast and highly efficient optical nonlinear response, and also provides a novel method for producing the same. is intended to provide.
上記問題点を解決するため、本発明による有機非線形光
学材料は、 下記−数式〔１〕（ただし、ＲおよびＲｏ
は、炭素数１８以下のアルキル基、Ａ−は疏水性アニオ
ンを表す。）で示されることを特徴としている。In order to solve the above problems, the organic nonlinear optical material according to the present invention has the following formula [1] (where R and Ro
represents an alkyl group having 18 or less carbon atoms, and A- represents a hydrophobic anion. ).
また、本発明による有機非線形光学材料の製造方法は、
−数式（Ｉｌｌで示される構造の化合物を原料とし、こ
れをゲル中で、疏水性アニオンにイオン交換することを
特徴としている。Furthermore, the method for producing an organic nonlinear optical material according to the present invention includes:
- It is characterized by using a compound having the structure represented by the formula (Ill) as a raw material and ion-exchanging it into a hydrophobic anion in a gel.
（Ｉｔ）
（ただしＲおよびＲｏは、炭素数１８以下のアルキル基
、Ｘ−はハロゲンイオンを示す）本発明をさらに詳しく
説明する。(It) (R and Ro are alkyl groups having 18 or less carbon atoms, and X- is a halogen ion) The present invention will be explained in more detail.
本発明の有機非線形光学材料は、下記−数式％式％
（ｒ）
上記式中、ＲおよびＲ”は、炭素数１８以下のアルキル
基である。炭素数が１８を越えると、合成が困難なうえ
、ゲル中での結晶化の際に、激しい会合が起こり、均一
は結晶作製が困難になる恐れを生じるからである。特に
好ましくは、炭素数が８以下である。最も好ましくはＲ
がエチル基、Ｒｏがメチル基の時、合成・結晶育成・非
線形光学効果のすべての面で、優れた材料が得られる。The organic nonlinear optical material of the present invention has the following formula: % Formula % (r) In the above formula, R and R'' are alkyl groups having 18 or less carbon atoms. In addition, during crystallization in the gel, intense association may occur, making it difficult to produce uniform crystals. Particularly preferably, the number of carbon atoms is 8 or less. Most preferably, R
When is an ethyl group and Ro is a methyl group, a material excellent in all aspects of synthesis, crystal growth, and nonlinear optical effects can be obtained.
Ｘ−は疏水性アニオンを表し、本発明においては疏水性
アニオンであれば、特に限定されるものではない。たと
えば実施例に示したｐ−トルエンスルホナート、テトラ
フェニルボレートなどの他、けい皮酸アニオン、各種カ
ルボン酸アニオンなどの一種以上であることができる。X- represents a hydrophobic anion, and in the present invention, it is not particularly limited as long as it is a hydrophobic anion. For example, in addition to p-toluenesulfonate and tetraphenylborate shown in the examples, it can be one or more of cinnamic acid anions, various carboxylic acid anions, and the like.
特にテトラフェニルボレートである時、化学的・物理的
に安定で、非線形光学効果の大きい良質の結晶材料が得
られる。In particular, when tetraphenylborate is used, a high-quality crystalline material that is chemically and physically stable and has a large nonlinear optical effect can be obtained.
本発明による有機非線形光学材料の主要な特徴は、π共
役低分子系化合物でありながら、従来のπ共役高分子を
上回る二次の非線形光学効果を有するだけでなく、従来
からイオン性結晶の欠点であった潮解性を大幅に低下さ
せ、実用材料としての要求条件を十分満足できるように
なった点にある。The main feature of the organic nonlinear optical material according to the present invention is that although it is a π-conjugated low-molecular compound, it not only has a second-order nonlinear optical effect that exceeds that of conventional π-conjugated polymers, but also has the drawbacks of conventional ionic crystals. The deliquescent property of this material has been significantly reduced, and it has become possible to fully satisfy the requirements for a practical material.
本発明の有機非線形光学材料〔１〕の製造にあたっては
、−数式ＣＩ＋）の化合物
〔■〕
（ただし、ＲおよびＲｏは、炭素数１８以下のアルキル
、；５．ｘ−はハロゲンイオンを示す）をゲル中で、前
記ハロゲンを疏水性アニオンにイオン交換することによ
って製造できる。In producing the organic nonlinear optical material [1] of the present invention, a compound [■] of formula CI+) (wherein R and Ro are alkyl having 18 or less carbon atoms; 5.x- represents a halogen ion) can be produced by ion-exchanging the halogen to a hydrophobic anion in a gel.
本発明による有機非線形光学材料の製造方法の主要な特
徴は、ゲル中にてイオン交換し、新規な有機非線形光学
材料を合成すると同時に良質の結晶材料が得られる点で
ある。The main feature of the method for producing an organic nonlinear optical material according to the present invention is that a novel organic nonlinear optical material can be synthesized by ion exchange in a gel, and at the same time, a high-quality crystalline material can be obtained.
ゲルを用いたイオン交換結晶化法については、１（、Ｋ
、ヘニッシェ著、中国一部・中田公子訳、“結晶成長と
ゲル法゛°、コロナ社刊、（１９７２）、に詳しい解説
がある。−船釣には、無機系イオン結晶の育成用として
、メタ・ケイ酸ナトリウムを主成分とするゲルが用いら
れているが、本発明による有機非線形光学材料の製造方
法においては、中性条件で容易にゲルを形成し、しかも
化学的に不活性なポリシロキサンゲルを用いることによ
って、良質大型結晶材料を得ることに成功したものであ
る。Regarding the ion exchange crystallization method using gel, 1(,K
A detailed explanation can be found in ``Crystal Growth and Gel Methods'' by Hennische, translated by Kimiko Nakata, published by Corona Publishing Co., Ltd. (1972). A gel containing sodium metasilicate as the main component is used, but in the method for producing an organic nonlinear optical material according to the present invention, a chemically inert polyester that easily forms a gel under neutral conditions is used. By using siloxane gel, we succeeded in obtaining a high quality large crystal material.
本発明による有機非線形光学材料を製造するにあたって
は特に以下の手順が有効である。すなわち、■Ｎ−アル
キルーＴ−ピコリニウムハライドとｐ−（Ｎ、Ｎ”−ジ
アルキルアミノ）ベンズアルデヒドを塩基触媒下で脱水
縮合する。再結晶により精製し、高純度のスチルバゾリ
ウムハライドを得る。■スチルバゾリウムハライドの溶
解したゲル上に、疏水性アニオン溶液を注ぎ、アニオン
が徐々にゲル中に拡１１シするように、２５±０． ５
°Ｃに設定した恒温槽に静置する。■−週間すると、ゲ
ル内に、最大３Ｘ３Ｘ０． ７ｍ”のスチルバゾリウム
テトラフェニルボレート〔１〕の単結晶が士数個得られ
る。ゲルの種類、溶媒の極性、ゲルの堅さ、スチルバゾ
リウムハライドや疏水性アニオンの濃度、育成ｍ度によ
り結晶成長の速度、結晶の形状、結晶の光学純度をコン
トロールすることができる。The following procedure is particularly effective in producing the organic nonlinear optical material according to the present invention. That is, (1) N-alkyl-T-picolinium halide and p-(N,N''-dialkylamino)benzaldehyde are dehydrated and condensed under a base catalyst. Purification is performed by recrystallization to obtain highly pure stilbazolium halide. ■Pour the hydrophobic anion solution onto the gel in which stilbazolium halide has been dissolved, and add 25±0.5 so that the anion gradually spreads into the gel.
Leave it in a constant temperature bath set at °C. - After a week, up to 3X3X0. Several 7 m" single crystals of stilbazolium tetraphenylborate [1] are obtained. Type of gel, polarity of solvent, hardness of gel, concentration of stilbazolium halide and hydrophobic anion, growth m The rate of crystal growth, crystal shape, and optical purity of the crystal can be controlled by controlling the degree of crystal growth.
以下、実施例に基づき本発明をさらに具体的に説明する
。Hereinafter, the present invention will be explained in more detail based on Examples.
〔実施例１〜２〕
常法に従って、Ｎ−メチル−γ−ピコリニウムアイオダ
イドとｐ−（Ｎ、Ｎ” −ジエチルアミノ）ベンズアル
デヒドをピペリジン存在下で脱水縮合し、Ｎ、 Ｎ’
−ジエチル−４−アミノ−Ｎ“−メチル−４゛−スチ
ルバゾリウム−アイオダイド（以下ＤＥＳ Ｉと略す）
を得た。このメタノール溶液に、テトラフェニルボレー
トメタノール溶液を加え、−夜装置した。析出固体（Ｎ
、 Ｎ”−ジエチル−４−アミノ−Ｎｏ−メチル−４°
−スチルバゾリウム−テトラフェニルボレート：以下ブ
ト略す）をろ取し二分して、一方をエタノール（〔実施
例１〕）、他方をアセトン：メタノール：ヘキサン１：
１：２（（実施例２〕）から再結晶した。[Examples 1 to 2] According to a conventional method, N-methyl-γ-picolinium iodide and p-(N,N''-diethylamino)benzaldehyde were dehydrated and condensed in the presence of piperidine to form N, N'
-diethyl-4-amino-N"-methyl-4"-stilbazolium iodide (hereinafter abbreviated as DES I)
I got it. A methanol solution of tetraphenylborate was added to this methanol solution, and the mixture was heated overnight. Precipitated solid (N
, N”-diethyl-4-amino-No-methyl-4°
-Stilbazolium-tetraphenylborate (hereinafter abbreviated as but) is collected by filtration and divided into two parts, one part is ethanol ([Example 1]), the other part is acetone: methanol: hexane: 1:
It was recrystallized from 1:2 ((Example 2)).
（実施例３〜５〕
実施例１にて合成したＤＥＳ Ｉを、テトラエトキシシ
ラン：メタノール：水に加え、完全に溶解させた。３０
°Ｃで一夜放置し、ゲル化が完了し、ゲル中にＤＥＳ
［の析出がないことを確かめた。(Examples 3 to 5) DES I synthesized in Example 1 was added to tetraethoxysilane:methanol:water and completely dissolved. 30
Leave to stand overnight at °C to complete gelation and DES in the gel.
It was confirmed that there was no precipitation of [.
ゲル上にテトラフェニルボレート溶液（メタノール：水
＝１ ： １）を注ぎ、２５±０．５°Ｃに設定した恒
温槽に一週間静置した。−週間後、ゲル内に成長した最
大３Ｘ３Ｘ０．７ｍｍ’のＤＥＳＴ単結晶が士数個得ら
れた。実施例３〜５における枯菌育成条件を下表に示す
。実施例５において、上記結晶を含め大型良質結晶が得
られた。A tetraphenylborate solution (methanol:water=1:1) was poured onto the gel, and the gel was left to stand in a constant temperature bath set at 25±0.5°C for one week. After - weeks, several DEST single crystals with a maximum size of 3X3X0.7 mm' were obtained, grown in the gel. The Bacillus subtilis growth conditions in Examples 3 to 5 are shown in the table below. In Example 5, large quality crystals including the above crystals were obtained.
（実施例６）
やや疏水性に劣るアニオンとして、Ｐ−）ルエンスルホ
ナートを用いて、〔製造例１〕と同様の方法で、ＤＥＳ
Ｉをアニオン交換し、Ｎ、 Ｎ’ −ジエチル−４−
アミノ−Ｎ”−メチル−４゛−スチルバゾリウム−Ｐ−
１−ルエンスルホナート（ＤＢＳ−ｐＴＳと略す）を得
た。メタノールで再結晶し、赤色板状晶を得た。(Example 6) DES was produced in the same manner as in [Production Example 1] using P-)luenesulfonate as an anion with slightly inferior hydrophobicity.
I was anion-exchanged to form N, N'-diethyl-4-
Amino-N"-methyl-4"-stilbazolium-P-
1-luenesulfonate (abbreviated as DBS-pTS) was obtained. Recrystallization from methanol gave red plate-like crystals.
〔比較例１〕
［実施例１］で合成したＤＢＳ ＋をメタノールから再
結晶し、赤色板状晶を得た。[Comparative Example 1] DBS + synthesized in [Example 1] was recrystallized from methanol to obtain red plate-like crystals.
〔比較例２）
（実施例１］と同様の操作で、Ｎ−メチル−Ｔ−ピコリ
ニウムアイオダイドとｐ−（Ｎ、Ｎ−ジメチルアミノ）
ベンズアルデヒドをピペリジン存在下で脱水縮合し、Ｎ
、 Ｎ−ジメチル−４−アミノ−Ｎｏ−メチル−４°−
スチルバゾリウム−アイオダイド（以下ＤＭＳ ＋と略
す）を得た。これをエタノールから再結晶し、赤色板状
晶を得た。[Comparative Example 2] In the same manner as in (Example 1), N-methyl-T-picolinium iodide and p-(N,N-dimethylamino)
Benzaldehyde is dehydrated and condensed in the presence of piperidine, and N
, N-dimethyl-4-amino-No-methyl-4°-
Stilbazolium iodide (hereinafter abbreviated as DMS+) was obtained. This was recrystallized from ethanol to obtain red plate-like crystals.
〔比較例３］
〔実施例１）と同様の方法で、ＤＭＳ Ｉをアニオン交
換し、Ｎ、 Ｎ−ジメチル−４−アミノ−Ｎｏ−メチル
−４゛ −スチルバゾリウム−テトラフェニルボレート
（ＤＭＳＴと略す）を得た。メタノールで再結晶し、赤
色板状晶を得た。アイオダイドで合成したＤＥＳ Ｉを
メタノールから再結晶し、赤色板状晶を得た。[Comparative Example 3] In the same manner as in [Example 1), DMSI was anion-exchanged to obtain N,N-dimethyl-4-amino-No-methyl-4'-stilbazolium-tetraphenylborate (abbreviated as DMST). I got it. Recrystallization from methanol gave red plate-like crystals. DES I synthesized with iodide was recrystallized from methanol to obtain red platelet crystals.
〔実施例１〜６、比較例１〜３のＳＨＯ相対強度および
ＴＨＧ相対強度の測定結果］
ＴＨＧ測定の方法は、以下に述べるとおりである。光源
には、Ｎｄ ： ＹＡＧレーザ−（波長１゜０６ ｔｔ
ｍ、 １０ Ｈｚ −８ＫＷ／ｃ＋ａ）を用い、可視
光をカットした後、レンズで集光したビームを試料に照
射し、試料より放射された光をモノクロメータに通して
、ＴＨＣ光（０，３５３μｍ）のみの強度をホトマルで
検知した。測定試料としては、実施例１〜６、比較例１
〜３の９種類を用意し、すべて１０５〜１２０μｍの粒
径に粉砕したものを用いた。さらに、観測されるＴＨＧ
光が、尿素やＭＮＡ （２−メチル−４−ニトロアニリ
ン）に見られるような二次のカスケード効果（ω＋２ω
）ではなく、純粋に三次の効果のみによることを確認す
るために、同一試料のＳＨＧについても測定した。[Measurement results of SHO relative intensity and THG relative intensity of Examples 1 to 6 and Comparative Examples 1 to 3] The method of THG measurement is as described below. The light source was a Nd: YAG laser (wavelength: 1°06 tt
After cutting off the visible light, the sample was irradiated with a beam focused by a lens, and the light emitted from the sample was passed through a monochromator to generate THC light (0,353 μm). ) was detected using a photomultiplier. Examples 1 to 6 and Comparative Example 1 were used as measurement samples.
3 to 3 were prepared, and all were ground to a particle size of 105 to 120 μm. Furthermore, the observed THG
Light causes a second-order cascade effect (ω+2ω
), and to confirm that this was due to a purely third-order effect, SHG of the same sample was also measured.
第２表
〔発明の効果〕
以上説明したように、本発明による有機非線形光学材料
およびその製造方法は、従来になく大きな三次の光非線
形有機結晶を提供するので、これを利用した光学素子、
例えば光双安定性素子、光スィッチ、光メモリなど将来
の光通信用集積素子の開発に極めて有効である。Table 2 [Effects of the Invention] As explained above, the organic nonlinear optical material and the method for producing the same according to the present invention provide a third-order optically nonlinear organic crystal that is larger than ever before, so optical elements using the same,
For example, it is extremely effective for the development of future optical communication integrated devices such as optical bistable devices, optical switches, and optical memories.
Claims (2)
基、Ａ＾−は疏水性アニオンを表す。）で示されること
を特徴とする有機非線形光学材料。(1) The following general formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [I] (However, R and R' are alkyl groups with 18 or less carbon atoms, and A^- represents a hydrophobic anion.) An organic nonlinear optical material characterized by:
、これをゲル中で、疏水性アニオンにイオン交換するこ
とを特徴とする有機非線形光学材料の▲数式、化学式、
表等があります▼ 〔II〕 （ただし、ＲおよびＲ’は、炭素数１８以下のアルキル
基、Ｘ＾−はハロゲンイオンを示す）（３）前記ゲルと
してポリシロキサンゲルであることを特徴とする特許請
求の範囲第２項記載の有機非線形光学材料の製造方法。(2) ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ [II] (However, R and R' are alkyl groups having 18 or less carbon atoms, and X^- represents a halogen ion.) (3) The gel is a polysiloxane gel. A method for producing an organic nonlinear optical material according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62264526A JPH01106022A (en) | 1987-10-20 | 1987-10-20 | Organic nonlinear optical material and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62264526A JPH01106022A (en) | 1987-10-20 | 1987-10-20 | Organic nonlinear optical material and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01106022A true JPH01106022A (en) | 1989-04-24 |
Family
ID=17404482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62264526A Pending JPH01106022A (en) | 1987-10-20 | 1987-10-20 | Organic nonlinear optical material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01106022A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5912257A (en) * | 1995-09-06 | 1999-06-15 | The Research Foundation Of State University Of New York | Two-photon upconverting dyes and applications |
-
1987
- 1987-10-20 JP JP62264526A patent/JPH01106022A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5912257A (en) * | 1995-09-06 | 1999-06-15 | The Research Foundation Of State University Of New York | Two-photon upconverting dyes and applications |
| US6402037B1 (en) | 1995-09-06 | 2002-06-11 | The Research Foundation Of State University Of New York | Two-photon upconverting dyes and applications |
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