JPH01124834A - Organic nonlinear optical material - Google Patents
Organic nonlinear optical materialInfo
- Publication number
- JPH01124834A JPH01124834A JP28222187A JP28222187A JPH01124834A JP H01124834 A JPH01124834 A JP H01124834A JP 28222187 A JP28222187 A JP 28222187A JP 28222187 A JP28222187 A JP 28222187A JP H01124834 A JPH01124834 A JP H01124834A
- Authority
- JP
- Japan
- Prior art keywords
- ring
- nonlinear optical
- compd
- effect
- org
- 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.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 21
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 32
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 239000000370 acceptor Substances 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 230000009022 nonlinear effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000003708 ampul Substances 0.000 description 4
- 230000009021 linear effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BAZVFQBTJPBRTJ-UHFFFAOYSA-N 2-chloro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CC=C(Cl)N=C1 BAZVFQBTJPBRTJ-UHFFFAOYSA-N 0.000 description 2
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- OZNXTQSXSHODFR-UHFFFAOYSA-N 1-chloroadamantane Chemical compound C1C(C2)CC3CC2CC1(Cl)C3 OZNXTQSXSHODFR-UHFFFAOYSA-N 0.000 description 1
- OFCBNMYNAHUDGE-UHFFFAOYSA-N 2-chloro-5-nitropyrimidine Chemical compound [O-][N+](=O)C1=CN=C(Cl)N=C1 OFCBNMYNAHUDGE-UHFFFAOYSA-N 0.000 description 1
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 1
- GZBKVUGZEAJYHH-UHFFFAOYSA-N 2-nitropyridin-3-amine Chemical compound NC1=CC=CN=C1[N+]([O-])=O GZBKVUGZEAJYHH-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- KQPKMEYBZUPZGK-UHFFFAOYSA-N 4-[(4-azido-2-nitroanilino)methyl]-5-(hydroxymethyl)-2-methylpyridin-3-ol Chemical compound CC1=NC=C(CO)C(CNC=2C(=CC(=CC=2)N=[N+]=[N-])[N+]([O-])=O)=C1O KQPKMEYBZUPZGK-UHFFFAOYSA-N 0.000 description 1
- 101001111984 Homo sapiens N-acylneuraminate-9-phosphatase Proteins 0.000 description 1
- 102100023906 N-acylneuraminate-9-phosphatase Human genes 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- WOLHOYHSEKDWQH-UHFFFAOYSA-N amantadine hydrochloride Chemical compound [Cl-].C1C(C2)CC3CC2CC1([NH3+])C3 WOLHOYHSEKDWQH-UHFFFAOYSA-N 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IZZMPZQAQTXAHW-UHFFFAOYSA-N bicyclo[2.2.1]heptan-3-amine;hydrochloride Chemical compound Cl.C1CC2C(N)CC1C2 IZZMPZQAQTXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、大きな元弁線形効果を有する有機元非線形元
学材料に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an organic nonlinear material having a large base linear effect.
（従来の技術）
従来、この棟の材料は、訪電体結晶例えばＬｉＮ１）Ｏ
３等が代表的でるるか、非線形光学効果を発現するため
には、非常に大きなパワーの光源が必要であり、半導体
レーザのような低出力の光源を用いて自由に非線形光学
効果を発現することができないという欠点があった〇一
方、大きな非線形光学効果ｔ−有する有機材料として例
えば、２−メチル−４−ニトロアニリン（以下ＭＮＡと
略記する）のような化合物が知られていた。(Prior art) Conventionally, the material of this ridge is a visiting body crystal such as LiN1)O
3rd grade is a typical example. In order to produce a nonlinear optical effect, a light source with extremely high power is required, and a low-power light source such as a semiconductor laser can be used to freely produce a nonlinear optical effect. On the other hand, a compound such as 2-methyl-4-nitroaniline (hereinafter abbreviated as MNA) was known as an organic material having a large nonlinear optical effect.
（発明が解決しようとする問題点）
しかしながら、大きなバルク単結晶を融液から得ようと
した場合、ＭＮＡなど従来から仰られていた材料では熱
分解などによって大きな単結晶を得ることが難しく、ま
たＭＮＡよりも更に大きい非線形光学効果を有する材料
の開発が望まれていた。(Problem to be solved by the invention) However, when trying to obtain a large bulk single crystal from a melt, it is difficult to obtain a large single crystal by thermal decomposition using conventional materials such as MNA. It has been desired to develop a material that has an even greater nonlinear optical effect than MNA.
本発明は、これら従来材料の欠点全解決するために提案
された化合物群で６り、その目的は光通信、元情報処理
分野における非線形光学効果を応用したデバイス用材料
を提供することにある。The present invention is a group of compounds proposed to overcome all the drawbacks of these conventional materials, and its purpose is to provide materials for devices that apply nonlinear optical effects in the fields of optical communications and information processing.
（問題点を解決する手段）
本発明を概説すれば、本発明は有機非線形光学材料に関
する発明であって、有機化合物系非線形光学材−科にお
いて該有機化合物が、下記−般式Ｉ：
、ｈ
（式中Ｘはビシクロ環あるいはトリシクロ環を示シ、電
はベンゼン環、ピリジン環、ピリミジン環などのに共役
系芳香環を示す）で表わされる化合物であることｔ特徴
とする。(Means for Solving Problems) To summarize the present invention, the present invention relates to an organic nonlinear optical material, and in the organic compound nonlinear optical material family, the organic compound has the following general formula I: , h (In the formula, X represents a bicyclo ring or tricyclo ring, and electron represents a conjugated aromatic ring such as a benzene ring, a pyridine ring, or a pyrimidine ring.)
本発明による有機元弁線形光学材料は、元弁線形効果を
もたらすπ共役系に結合したドナー、アクセプターのう
ち、ドナーがかさ高なビシクロ環、あるいはトリシクロ
環で構成されているため、アミ７基窒素に結合する水素
に基づく水素結合効果と併せ、反転対称社の結晶構造と
なることなく尖きい二次の非線形光学効♂−現す△
ることが可能となっている。In the organic linear optical material according to the present invention, among the donors and acceptors bonded to the π-conjugated system that produces the linear effect, the donor is composed of a bulky bicyclo ring or tricyclo ring. In combination with the hydrogen bonding effect based on hydrogen bonding to nitrogen, it is possible to exhibit sharp second-order nonlinear optical effects without forming an inversion-symmetric crystal structure.
のビシクロ環、トリシクロ環である。通常はこれらビシ
クロ環、トリシクロ環のアミン化合物を原料として目的
とする有機光非線形光学材料を得ることができる。また
、これらシクロ環のアミン部位以外の位置への置換基の
導入は、得られた結晶に反転対称構造金４たらさない限
りにおいては、無置換の場合同様良好な効果を与える。Bicyclo ring, tricyclo ring. Usually, the desired organic optical nonlinear optical material can be obtained using these bicyclo- and tricyclo-ring amine compounds as raw materials. In addition, the introduction of a substituent to a position other than the amine site of these cyclocycles has the same good effect as the case of no substitution, as long as the inverted symmetric gold 4 structure is not imparted to the obtained crystal.
この様な置換基としてはメチル基などのアルキル基、゛
メトキシ基などのアルコキシ基、水酸基、ハロゲンなど
がるる。更に、ｔで示されるベンゼン環、ピリジン環、
ピリミジン環などのｔ共役系芳香環のニトロ部位、アミ
ン部位以外の位置への置換基の導入によって、更に大き
い非線形光学効果を得ると共に、結晶性の一層の向上を
図ることも可能でるる。そのような置換基としてはクロ
ルなどの／１０ゲン類、アセトアミド基、水酸基のよう
な水素結合性置換基、メチル基、メトキシ基の様なアル
キル基、アルコキシ基が挙げられる。Examples of such substituents include alkyl groups such as methyl groups, alkoxy groups such as methoxy groups, hydroxyl groups, and halogens. Furthermore, a benzene ring, a pyridine ring represented by t,
By introducing a substituent at a position other than the nitro site or amine site of a t-conjugated aromatic ring such as a pyrimidine ring, it is possible to obtain a larger nonlinear optical effect and to further improve crystallinity. Examples of such substituents include /10 groups such as chloro, hydrogen bonding substituents such as acetamido groups and hydroxyl groups, alkyl groups such as methyl groups and methoxy groups, and alkoxy groups.
一方、大きな単結晶の育成が報告されているブリッジマ
ン法は、融液からの単結晶育成法であり、本発明の２−
アダマンクンアミノ−５−二トロビリジン（以下ＡＡＮ
Ｐと略記する）にもこの方法が適用できる。実際に以下
に示すような工程によりＡＡＮＰの単結晶を育成した。On the other hand, the Bridgman method, which has been reported to grow large single crystals, is a method for growing single crystals from a melt.
adamancun amino-5-nitroviridine (hereinafter referred to as AAN)
This method can also be applied to (abbreviated as P). A single crystal of AANP was actually grown through the steps shown below.
第１図に示すのは、本発明におけるＡＡＮＰの単結晶育
成炉の断面概略図である。１は炉心管、２は上部ヒータ
、３は下部ヒータ、４は結晶育成ガラスアンプル、５は
ＡＡＮＰの単結晶部、６はＡＡＮＰの融液部、７は４を
下降させるための結晶引き下げ系である。FIG. 1 is a schematic cross-sectional view of an AANP single crystal growth furnace according to the present invention. 1 is a furnace core tube, 2 is an upper heater, 3 is a lower heater, 4 is a crystal growth glass ampoule, 5 is a single crystal part of AANP, 6 is a melt part of AANP, and 7 is a crystal pulling system for lowering 4. be.
以下、前記一般式ｌで表わされる化合物の製造例を具体
的に説明するが、本発明はこれらに限定されない。Hereinafter, production examples of the compound represented by the general formula 1 will be explained in detail, but the present invention is not limited thereto.
製造例１２−アダマンタンアミノ゛−５−二トロピリジ
ン（ＡＡＮＰ ）の合成
２−クロロ−５−ニトロピリジン１０ ｍｍｏｌと１−
アダマンタンアミン１１ ｍｍｏｌ ｆ ） ’）エ
チルアミンに浴解し、窒素雰囲気下で一昼夜加熱還流を
行って反応物を得る。反応液を室温まで冷却し、生成物
を完全に析出させた後、これをろ別し、冷エタノールに
て洗浄全行った。ぺンゼンを用いて再結晶し、粒状結晶
を得た〇製造例２ ４−（５−ノルアダマンタンアミノ
）ニトロベンゼン（以下ＮＡＡＮＢと略
記する）の合成
４−クロロニトロベンゼン１０ ｍｍｏｌ と３−ノ
ルアダマンタンアミン１１ ｍ！１１０１ をジメチル
スルホキシドに溶解し、炭酸カリウム存在下で一昼夜加
熱還流を行って反応物を得る。製造例１と同様に１冷却
、洗浄後ベンゼンを用いて再結晶を行い粒状結晶を得た
。Production Example 1 Synthesis of 2-adamantanamino-5-nitropyridine (AANP) 10 mmol of 2-chloro-5-nitropyridine and 1-
Adamantaneamine (11 mmol f) ') is dissolved in ethylamine and heated under reflux for one day under a nitrogen atmosphere to obtain a reaction product. After the reaction solution was cooled to room temperature and the product was completely precipitated, it was filtered and washed with cold ethanol. Recrystallization was performed using penzene to obtain granular crystals. Production Example 2 Synthesis of 4-(5-noradamantanamino)nitrobenzene (hereinafter abbreviated as NAANB) 4-chloronitrobenzene 10 mmol and 3-noradamantanamine 11 m! 1101 was dissolved in dimethyl sulfoxide and heated under reflux for one day in the presence of potassium carbonate to obtain a reaction product. After 1 cooling and washing in the same manner as in Production Example 1, recrystallization was performed using benzene to obtain granular crystals.
製造例３〜５
製造例１と同様に、３−ノルアダマンタンアミン、２−
アダマンタンアミンーハイドロクロラ゛イド、２−ノル
ボルナンアミン−ハイドロクロライドを原料として、対
応するアミノニトロピリジン（各ｋＮＡＡＮＰ、２ＡＡ
ＮＰ、ＮＡＮＰと略記する）を合成し、結晶を得た０
製造例６
製造例２と同様に、１−アダマンタンアミンｔ−［科と
して、対応するアミノニトロベンゼン（ＡＡＮＢと略記
する）ｔ−合成し、結晶を得た。Production Examples 3 to 5 Similar to Production Example 1, 3-noradamantanamine, 2-
Using adamantanamine-hydrochloride and 2-norbornanamine-hydrochloride as raw materials, the corresponding aminonitropyridine (each kNAANP, 2AA
NP, NANP) were synthesized and crystals were obtained.0 Production Example 6 In the same manner as Production Example 2, 1-adamantanamine t- [as a family, the corresponding aminonitrobenzene (abbreviated as AANB) t- was synthesized. , obtained crystals.
製造例７２−アダマンタンアミノ−５−二トロビリミジ
ン（ＡＡＮＰＹと略記する）の合成
製造例１において、２−クロロ−５−ニトロピリジンの
代わりに２−クロロ−５−ニトロピリミジンを用いたほ
かは製造例１と同様の方法によって、ＡＡＮＰＹを合属
し、結晶を得た。Production Example 7 Synthesis of 2-adamantanamino-5-nitropyrimidine (abbreviated as AANPY) Production example 1 except that 2-chloro-5-nitropyrimidine was used instead of 2-chloro-5-nitropyridine. AANPY was combined by the same method as in 1 to obtain crystals.
製造例８〜９
２−／ロウ−４−ニトロアニリンと２−クロロノルボル
ナン’１ＮａＯＨ存在下でアセトン中で加熱還流を行っ
たほかは製造例２と同様の方法によって、３−クロロ−
４−ノルボルナンアミノニトロベンゼン（ＣＮＡＮＢと
略記する）全会成し、結晶を得た。Production Examples 8 to 9 3-chloro-
4-Norbornane aminonitrobenzene (abbreviated as CNANB) was completely synthesized to obtain crystals.
また、同様の方法によって１−クロロアダマンタンを用
いて、３−クロロ−４−アダマンタンアミノニトロベン
ゼン（ＣＡＡＮＢと略記スル）上台成し、結晶を得た。In addition, 3-chloro-4-adamantanaminonitrobenzene (abbreviated as CAANB) was formed on 3-chloro-4-adamantanaminonitrobenzene (abbreviated as CAANB) using 1-chloroadamantane in a similar manner to obtain crystals.
（実施Ｎ）
以下、本発明を実施レリにより、史に具体的に説明する
が、本発明はこれら実施例に限定されない０
実施例１〜９
製造例１〜９で得られた化合物について非線形光学％性
を測定した。非線形光学効果の大きさは、以下に記載す
るようにクルツ（Ｋｕｒｔｚ ）らによって確立された
パウダー法を用いた。基本波波長１．０６ ＡｍのＮｄ
：ＹＡＧレーザ（ＩＯＨｓ？。(Execution N) Hereinafter, the present invention will be explained in detail based on practical examples, but the present invention is not limited to these examples. Examples 1 to 9 Nonlinear optical analysis of the compounds obtained in Production Examples 1 to 9 % properties were measured. The magnitude of the nonlinear optical effect was determined using the powder method established by Kurtz et al., as described below. Fundamental wave wavelength 1.06 Am Nd
:YAG laser (IOHs?
５０ ＭＷ／ｃｍ” ） ｆ光源とし、可視光をカット
したのち、レンズで集光したビームを微結晶粉末試料に
照射する。試料より放射された元をＸＲカットフィルタ
及びモノクロメータを通し、発生する第二′？１６１ｍ
波（８ＨＧ）の強度金７オトマルで検出した。結果は、
標準試料である尿素の微結晶粉末試料における８ＨＧ強
度に対する比で評価した。結果を下記の表１に示す。な
お、比較例として、ＭＮＡの結果を併記した。50 MW/cm") f light source, and after cutting off visible light, the beam focused by a lens is irradiated onto the microcrystalline powder sample. The source emitted from the sample is passed through an XR cut filter and a monochromator, and the generated light is 2nd'?161m
The intensity of the wave (8HG) was detected with gold 7 otomaru. Result is,
Evaluation was made based on the ratio to the 8HG intensity in a standard sample of urea microcrystalline powder. The results are shown in Table 1 below. In addition, as a comparative example, the results of MNA are also shown.
表１ ８ＨＧ測定結果
ＳＨＧ強匿は表１に示す様にＡＡＮ Ｐは泳索比２００
倍という大きい値であシ、このほか２ＡＡＮＰでも１８
０倍、ＣＡＡＮＢで１６０倍、ＮＡＡＮＰで１５０倍、
ＡＡＮＰＹで９０倍、ＣＮＡＮＢで６０倍、ＡＡＮＢで
５０倍、ＮＡＡＮＢが４５倍というように、ＭＮＡに比
べはるかに大きい値が得られている。Table 1 8HG measurement results SHG strength is as shown in Table 1, AAN P has a swimming ratio of 200
In addition to this, 2AANP also has a large value of 18
0x, 160x for CAANB, 150x for NAANP,
Much larger values than MNA have been obtained, such as 90 times higher for AANPY, 60 times higher for CNANB, 50 times higher for AANB, and 45 times higher for NAANB.
実施例１０
第１図に示した装置を用い、以下の様にしてＡＡＮＰの
単結晶を得た。第１図における２のヒータはＡＡＮＰの
融点（１６５℃）より１０℃高い１７５±１℃に設定し
、３のヒータは融点よシ２０℃低い１４５±１℃に設定
した。まず始めに、４の結晶育成ガラスアンプルｔ−製
作し、このアンプル中にＡＡＮＰ １０ ｆ ｉｉｌ素
雰囲気下で封入した。このアンプル’ｋｂ第１図の結晶
育成炉中ｔ１■／ ｈｒでゆつくシ下降させた。次に、
４ｔ−ヒータ３の位置で一旦止め、５ Ｃ／ｈｒで室温
までゆつくり冷却し、結晶七収９出した◎はぼ、管全体
で単結晶が育成されており、大きさは直径１５■、長さ
３０■のＡＡＮＰ単結晶であった〇
この単結晶の熱的な安定性、特に融点以上に加温した場
合の構造変化ｔ−ＩＲ，ＮＭＲにより満ぺた。融点１６
５℃より２０℃高い温度でＡＡＮＰ ｔ−２４時間放置
したが、構造上の変化はなかった。これに対し、ＭＮＡ
の場合、融点１３１℃より２０℃高い温度で２４時間放
置したところ、融液が黒褐色に変化しておシ、構造上の
変化が生じていた。以上のことから、 ＡＡＮＰはＭＮ
Ａよシ熱的に安定でおることがわかった。Example 10 Using the apparatus shown in FIG. 1, a single crystal of AANP was obtained in the following manner. Heater No. 2 in FIG. 1 was set at 175±1° C. which was 10° C. higher than the melting point of AANP (165° C.), and heater No. 3 was set at 145±1° C. which was 20° C. lower than the melting point of AANP. First, a crystal growth glass ampoule No. 4 was prepared, and AANP 10 fiil was sealed in this ampoule in an elementary atmosphere. This ampoule 'kb was slowly lowered into the crystal growth furnace shown in Figure 1 at t1/hr. next,
Once stopped at the 4t heater 3 position, the tube was slowly cooled down to room temperature at 5 C/hr, and a crystal yield of 7.9 was obtained.A single crystal was grown in the entire tube, and the size was 15 cm in diameter. It was an AANP single crystal with a length of 30 cm. The thermal stability of this single crystal, especially the structural change when heated above the melting point, was satisfactory based on t-IR and NMR. melting point 16
Although AANP was left at a temperature 20°C higher than 5°C for 24 hours, there was no structural change. On the other hand, MNA
In the case of , when the melt was left for 24 hours at a temperature 20°C higher than the melting point of 131°C, the melt turned dark brown and structural changes occurred. From the above, AANP is MN
It was found that A was thermally stable.
本発明による他の有機元弁線形光学材料についても同様
に大きなバルク結晶が得られる順向がめった。Similar progress has been made in obtaining large bulk crystals for other organic base linear optical materials according to the present invention.
また、本発明による有機非線形光学材料詳は、溶媒から
の再結晶法によっても大型バルク結晶が得られると共に
、通常の真空蒸着法による薄膜形成が容易な材料である
ことがわかった。Furthermore, it has been found that the organic nonlinear optical material according to the present invention can be used to obtain large bulk crystals by recrystallization from a solvent, and is also a material that can be easily formed into a thin film by ordinary vacuum evaporation.
（発明の効果）
以上説明したように、本発明による化合物群は、非線形
光学効果が大きく、シかも大きなバルク結晶が得られる
ことから、非腺形光学効果を応用したデバイス、例えば
波長変換素子、光変調器、元スイッチ、更には光双安定
素子等を構築する上での重要な材料となｐうる利点があ
る０(Effects of the Invention) As explained above, the compound group according to the present invention has a large nonlinear optical effect and a large bulk crystal can be obtained. It has the advantage of being an important material in constructing optical modulators, switches, and even optical bistable devices.
第１図は、本発明においてＡＡＮＰの単結晶を育成する
装置の＃面概略図でめる０
１：炉心管、２：上部ヒータ、３：下部ヒータ、４：結
晶育成ガラスアンプル、 ５ ： ＡＡＮＰの単結晶部
、６ ： ＡＡＮＰの融敵部、７：結晶引き下げ系
特許出願人 日本電信電話株式会社FIG. 1 shows a # side schematic diagram of an apparatus for growing a single crystal of AANP in the present invention. 6: AANP's ally, 7: Crystal pulling system patent applicant Nippon Telegraph and Telephone Corporation
Claims (1)
物が下記一般式 I ： ▲数式、化学式、表等があります▼…〔 I 〕 （式中Ｘはビシクロ環あるいはトリシクロ環を示し、ｘ
はｚ共役系芳香環を示す）で表わされる化合物であるこ
とを特徴とする有機非線形光学材料。[Claims] 1. In an organic compound-based nonlinear optical material, the organic compound has the following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, X represents a bicyclo ring or a tricyclo ring. indicate, x
is a z-conjugated aromatic ring).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28222187A JPH071360B2 (en) | 1987-11-10 | 1987-11-10 | Organic nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28222187A JPH071360B2 (en) | 1987-11-10 | 1987-11-10 | Organic nonlinear optical material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01124834A true JPH01124834A (en) | 1989-05-17 |
| JPH071360B2 JPH071360B2 (en) | 1995-01-11 |
Family
ID=17649635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28222187A Expired - Lifetime JPH071360B2 (en) | 1987-11-10 | 1987-11-10 | Organic nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH071360B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981756A (en) * | 1996-11-15 | 1999-11-09 | Nippon Telegraph And Telephone Corporation | Deuterated 2-adamantylamino-5-nitropyridine, organic nonlinear optical material containing the compound, and production method of the compound |
| WO2021263164A1 (en) * | 2020-06-25 | 2021-12-30 | Lightwave Logic, Inc. | Nonlinear optical chromophores comprising a diamondoid group |
-
1987
- 1987-11-10 JP JP28222187A patent/JPH071360B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981756A (en) * | 1996-11-15 | 1999-11-09 | Nippon Telegraph And Telephone Corporation | Deuterated 2-adamantylamino-5-nitropyridine, organic nonlinear optical material containing the compound, and production method of the compound |
| WO2021263164A1 (en) * | 2020-06-25 | 2021-12-30 | Lightwave Logic, Inc. | Nonlinear optical chromophores comprising a diamondoid group |
| US11921401B2 (en) | 2020-06-25 | 2024-03-05 | Lightwave Logic, Inc. | Nonlinear optical chromophores having a diamondoid group attached thereto, methods of preparing the same, and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH071360B2 (en) | 1995-01-11 |
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