JPH02238443A - Organic nonlinear optical material - Google Patents
Organic nonlinear optical materialInfo
- Publication number
- JPH02238443A JPH02238443A JP5827389A JP5827389A JPH02238443A JP H02238443 A JPH02238443 A JP H02238443A JP 5827389 A JP5827389 A JP 5827389A JP 5827389 A JP5827389 A JP 5827389A JP H02238443 A JPH02238443 A JP H02238443A
- Authority
- JP
- Japan
- Prior art keywords
- nonlinear optical
- group
- electron
- general formula
- compound represented
- 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 70
- 239000000463 material Substances 0.000 title claims abstract description 33
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 125000004434 sulfur atom Chemical group 0.000 abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 78
- -1 trifluoroethanesulfonyl Chemical group 0.000 description 68
- 239000013078 crystal Substances 0.000 description 14
- 229920000106 Liquid crystal polymer Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 230000005684 electric field Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- PTBKFATYSVLSSD-ZZXKWVIFSA-N (ne)-n-[(5-nitrofuran-2-yl)methylidene]hydroxylamine Chemical compound O\N=C\C1=CC=C([N+]([O-])=O)O1 PTBKFATYSVLSSD-ZZXKWVIFSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008247 solid mixture Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- 150000000565 5-membered heterocyclic compounds Chemical class 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000001691 aryl alkyl amino group Chemical group 0.000 description 2
- 125000004659 aryl alkyl thio group Chemical group 0.000 description 2
- 125000001769 aryl amino group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 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 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-SCSAIBSYSA-N (2R)-butan-2-ol Chemical compound CC[C@@H](C)O BTANRVKWQNVYAZ-SCSAIBSYSA-N 0.000 description 1
- GDVSGAURQOZZGU-UHFFFAOYSA-N 2-(methylamino)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(NC)=CC=C3C(=O)C2=C1 GDVSGAURQOZZGU-UHFFFAOYSA-N 0.000 description 1
- JIFVPBALUHDGEP-UHFFFAOYSA-N 2-[(4-methylphenyl)methylidene]propanedinitrile Chemical compound CC1=CC=C(C=C(C#N)C#N)C=C1 JIFVPBALUHDGEP-UHFFFAOYSA-N 0.000 description 1
- SITKZBWMJBVSID-UHFFFAOYSA-N 2-bromo-n,n-dimethyl-4-nitroaniline Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=C1Br SITKZBWMJBVSID-UHFFFAOYSA-N 0.000 description 1
- SXINBFXPADXIEY-UHFFFAOYSA-N 5-Nitrofurfural Chemical compound [O-][N+](=O)C1=CC=C(C=O)O1 SXINBFXPADXIEY-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010011878 Deafness Diseases 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GKOSPEZZNQBUPQ-UHFFFAOYSA-N N-[(3-nitrofuran-2-yl)methylidene]hydroxylamine Chemical compound [N+](=O)([O-])C1=C(C=NO)OC=C1 GKOSPEZZNQBUPQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005138 alkoxysulfonyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005098 aryl alkoxy carbonyl group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 231100000895 deafness Toxicity 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- SVTDYSXXLJYUTM-UHFFFAOYSA-N disperse red 9 Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC SVTDYSXXLJYUTM-UHFFFAOYSA-N 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 208000016354 hearing loss disease Diseases 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RPLYOMTWLVLZQL-UHFFFAOYSA-N n-(4-butoxyphenyl)-1-(2-nitrophenyl)methanimine Chemical compound C1=CC(OCCCC)=CC=C1N=CC1=CC=CC=C1[N+]([O-])=O RPLYOMTWLVLZQL-UHFFFAOYSA-N 0.000 description 1
- PINNQKFNRKECFX-UHFFFAOYSA-N n-ethyl-1,3,4-thiadiazol-2-amine Chemical compound CCNC1=NN=CS1 PINNQKFNRKECFX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000001400 nonyl 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])C([H])([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
- 239000011368 organic material Substances 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N p-hydroxybiphenyl Natural products C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl 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])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
- 239000012071 phase Substances 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000000213 sulfino group Chemical group [H]OS(*)=O 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
く産業上の利用分野〉
本発明はオブトエレクトロニクス分野で好適に使用され
る有機非線形光学材料に関する。DETAILED DESCRIPTION OF THE INVENTION Industrial Application Field The present invention relates to an organic nonlinear optical material suitably used in the field of electronics.
く従来技術及び発明が解決しようとする問題点〉非線形
光学効果は、媒質に光が入射したとき、その光の電場の
２乗以上の高次の項に比例する分極が生じる現象であり
、レーザ光等の強電界下では非線形光学効果か顕著に現
れる。この非線形光学効果により、第２高調波発生、力
一効果、光双安定などが可能となり、特に光の電場の２
乗に比例して起る２次非線形光学効果は光波長変換素子
、光変調素子等の非線形光学素子としてオプトエレクト
ロニクス分野の発展を約束する素子への応用が可能であ
るため多くの注目を集めている。Prior Art and Problems to be Solved by the Invention> The nonlinear optical effect is a phenomenon in which when light enters a medium, polarization occurs that is proportional to a higher-order term equal to or higher than the square of the electric field of the light. Under strong electric fields such as light, nonlinear optical effects become noticeable. This nonlinear optical effect enables second harmonic generation, the Force-Unit effect, optical bistability, etc., and especially the
The second-order nonlinear optical effect, which occurs in proportion to the second power, has attracted a lot of attention because it can be applied to nonlinear optical elements such as optical wavelength conversion elements and optical modulation elements, which promise the development of the optoelectronics field. There is.
それらの素子を構成する材料は、現在のところＫ Ｈ
２ Ｐ Ｏ ４ （ Ｋ Ｄ Ｐ ）などの一部の無
機材料か実用されているにすぎない。しかし、それら無
機材料の非線形光学定数は小さく、それゆえ素子の動作
には極めて高い電圧、または極めて強い光強度が必要で
あった。このため、非線形光学定数の大きい材料への要
求は極めて強く、様々な材料探索がなされてきた。無機
材料においては、ニオブ酸リチウム（Ｌ ｉＮｂｏ３）
が最も大きい非線形光学定数を有しているが、ニオブ酸
リチウムは強いレーザ光を照射すると部分的に屈折率の
変化を生じ、また光で容易にｔｉ傷する欠点を有してお
り未だ実用化されていない。The materials that make up these elements are currently KH
Only some inorganic materials such as 2PO4 (KDP) are in practical use. However, the nonlinear optical constants of these inorganic materials are small, and therefore extremely high voltage or extremely strong light intensity is required to operate the device. For this reason, there is an extremely strong demand for materials with large nonlinear optical constants, and various materials searches have been made. Among inorganic materials, lithium niobate (L iNbo3)
has the largest nonlinear optical constant, but lithium niobate has the disadvantage that its refractive index partially changes when irradiated with strong laser light, and it is easily damaged by light, so it is still not in practical use. It has not been.
近年になって、無機系材料に比べて有機系材料の方かは
るかに高い非線形光学特性を有することが見出だされ、
例えば、２−メチル−４一二１・ロアニリン（ＭＮＡ）
に代表されるように、π電子系を有すると共に分子内に
電子供与性基と電子吸引性基とを有し、極めて大きい非
線形光学定数を有する材料が注目されている。しかし、
２次の非線形光学効果を得るためには、結晶構造が反転
対称中心を持たないことが必要であり、さらに結晶内の
分子か一方向に並んだ構造が理想的であるが、２次の非
線形光学定数β（以下、非線形光学定数βと称する）が
分子状態でＭＮＡに比べて大きい化合物、即ち、より大
きい永久双極子モーメント、またより大きいπ電子系を
有する化合物の結晶構造を制御することは極めて困難で
あり、今までＭＮＡより高い２次非線形光学効果を有す
，る有機化合物の報告例はほとんどなく、従って、ＭＮ
Ａより高効率の有機非線形光学材料は知られていない。In recent years, it has been discovered that organic materials have much higher nonlinear optical properties than inorganic materials.
For example, 2-methyl-4-21-roaniline (MNA)
Materials that have a π-electron system, an electron-donating group and an electron-withdrawing group in the molecule, and have extremely large nonlinear optical constants are attracting attention, as typified by . but,
In order to obtain a second-order nonlinear optical effect, it is necessary for the crystal structure to have no center of inversion symmetry, and ideally the molecules within the crystal are aligned in one direction, but the second-order nonlinear optical effect It is possible to control the crystal structure of a compound whose optical constant β (hereinafter referred to as nonlinear optical constant β) is larger than that of MNA in the molecular state, that is, a compound having a larger permanent dipole moment and a larger π electron system. This is extremely difficult, and until now there have been few reports of organic compounds that have higher second-order nonlinear optical effects than MNA.
No organic nonlinear optical material with higher efficiency than A is known.
本発明は上記問題点に鑑みてなされたものであり、高い
非線形光学効果を有する有機非線形光学材料を提供する
ことを目的とする。The present invention has been made in view of the above problems, and an object of the present invention is to provide an organic nonlinear optical material having high nonlinear optical effects.
く問題点を解決するための手段および作用〉本発明の有
機非線形光学材料は、少なくとも下記一般式［Ｉ］で表
される化合物を含有することを特徴とする。Means and Effects for Solving Problems> The organic nonlinear optical material of the present invention is characterized by containing at least a compound represented by the following general formula [I].
（式中、Ｘは電子吸引性基、Ｙは電子供与性基、Ｚはへ
テロ原子を示す。）
有機非線形光学材料において、非線形光学定数βを大き
くするには、光の電場により分極か生ずる際に、分子内
の電子移動がスムーズに進行することが必要とされるが
、本発明は上記の構成よりなり、一般式（Ｉ）で表され
る複素５員環化合物は、複素５員環骨格が電子供与性基
と電子吸引性基を含む置換基とを有しているので、電子
遷移に伴なって電子が大きく移動し、分子レベルでの非
線形光学定数βが大きく、顕著な非線形光学効果を示す
。(In the formula, X is an electron-withdrawing group, Y is an electron-donating group, and Z is a heteroatom.) In organic nonlinear optical materials, in order to increase the nonlinear optical constant β, polarization is caused by the electric field of light. In this case, it is necessary that the intramolecular electron transfer proceeds smoothly, and the present invention has the above structure, and the 5-membered heterocyclic compound represented by the general formula (I) is a 5-membered heterocyclic compound. Since the skeleton has an electron-donating group and a substituent containing an electron-withdrawing group, electrons move greatly due to electron transition, and the nonlinear optical constant β at the molecular level is large, resulting in remarkable nonlinear optical properties. Show effectiveness.
なお、前記一般式（Ｉ）で表される化合物において、Ｘ
か水素原子または５位に置換したニトロ基、Ｙかアルコ
キシル基またはヒドロキシル基、特にヒドロキシル基で
あり、Ｚが酸素原子または硫黄原子であるものが、電子
移動度か大きく、非線形光学定数βを大きくする上で好
ましい。特に上記化合物の単一成分結晶からなる非線形
光学材料は、さらに非線形光学定数が大きく、有機非線
形光学材料として好ましい。In addition, in the compound represented by the general formula (I), X
A hydrogen atom or a nitro group substituted at the 5-position, an alkoxyl group or a hydroxyl group, especially a hydroxyl group, and those in which Z is an oxygen atom or a sulfur atom have a large electron mobility and a large nonlinear optical constant β. It is preferable to do so. In particular, a nonlinear optical material made of a single-component crystal of the above compound has a larger nonlinear optical constant and is preferable as an organic nonlinear optical material.
以下に本発明を詳細に説明する。The present invention will be explained in detail below.
前記一般弐ｍで表される化合物において、電子吸引性基
Ｘとしては、例えば、フッ素、塩素、臭素、ヨウ素など
のハロゲン原子；シアノ基；ニトロ基；メタンスルホニ
ル、エタンスルホニル、ブロバンスルホニル、ブタンス
ルホニル、トリフルオロメタンスルホニル、２，２．２
−｝リフルオロエタンスルホニルなどのハロゲン原子を
有していてもよいアルカンスルホニル基；スルホニル基
；メトキシスルホニル、エトキシスルホニル、プロポキ
シスルホニル、イソプロポキシスルホニル、ブトキシス
ルホニル、ｔｅｒｔ−ブトキシスルホニル、ペンチルオ
キシスルホニル、ヘキシルオキシスルホニル、オクチル
オキシスルホニルなどのアルコキシスルホニル、フエノ
キシスルホニル、ｐ−シアノフエノキシスルホニルなど
の置換基を有していてもよいフェノキシスルホニル等の
エステル化されたスルホニル基；カルボキシル基；メト
キシ力ルボニル、エトキシ力ルボニル、プロポキシカル
ボニル、イソブロポキシカルボニル、ブトキシ力ルボニ
ル、イソブトキシカルボニル、ｔｅｒｔ−ブトキシ力ル
ボニル、ヘキシルオキシ力ルボニル、ヘブチルオキシ力
ルボニル、オクチルオキシ力ルボニル、ノニルオキシ力
ルボニル、デンルオキシ力ルボニル、ウンデシルオキシ
力ルボニル、ドデシルオキシ力ルボニル、トリデシルオ
キシ力ルボニル、テトラデシルオキシ力ルボニル、ペン
タデシルオキシ力ルボニルなどのアルコキシ力ルボニル
基、フエノキシ力ルボニル、ｐ−ニトロフエノキシカル
ボニルなどの置換基を有していてもよいアリールオキシ
カルボニル、ペンジルオキシ力ルボニル、ペンズヒドリ
ルオキシカルボニルなどのアラルキルオキシ力ルボニル
等のエステル化されたカルボキシル基；ホルミル、アセ
チル、プロビオニル、ブチリル、ヘキサノイル、ベンゾ
イルなどのアシル基；カルバモイル、メチル力ルバモイ
ル、ジメチルカルバモイル、エチル力ルバモイル、プロ
ビル力ルバモイル、フエニルカルバモイル、ベンジルカ
ルバモイルなどの置換基を有していてもよいカルバモイ
ル基；スルファモイル、メチルスルファモイル、エチル
スルファモイル、フエニルスルファモイル、ベンジルス
ルファモイルなどの置換基を有していてもよいスルファ
モイル基；ニトロソ基；スルフィノ基；チオカルボキシ
ル基：基
（式中、Ａはシアノ基、カルボキシル基またはアルコキ
ンカルボニル基を示し、Ｒ１は水素原子またはアルキル
基を示す）、例えば、２，２−ジカルボキシビニル、２
−カルボキシ−２−メトキシ力ルポニルビニル、２−カ
ルボキシ−２−エトキシ力ルポニルビニル、２−カルボ
キシ−２−プロボキシカルポニルビニル、２−カルボキ
シ−２イソブロポキシカルボニルビニル、２，２−ジメ
トキシ力ルポニルビニル、２．２−エトキシ力ルポニル
ビニル、２ ２−ジプロボキシ力ルポニルビニル、２．
２−ジイソプ口ポキシ力ルポニルビニル、２−メトキシ
力ルボニル−２−エトキシ力ルポニルビニル、２−メト
キシ力ルボニル−２＝プロポキシカルポニルビニル、２
−エトキシ力ルボニル−２−プロポキシカルポニルビニ
ル、２一エトキシ力ルボニル−２−イソブロポキシカル
ボニルビニル、２．２−ジブトキシ力ルポニルビニル、
２．２−ジイソブトキシ力ルポニルビニル、２．２−ジ
ーｔｅｒｔ−ブトキシ力ルポニルビニル、２．２−ジペ
ンチルオキシ力ルボニル．ビニル、２．２−ジヘキシル
オキシ力ルポニルビニル、２．２一ジヘプチルオキシカ
ルボニルビニル、２．２−ジオクチルオキシ力ルポニル
ビニル、２，２−ジノニルオキシ力ルポニルビニル、２
．２−ジデシルオキシ力ルポニルビニル、２．２−ジウ
ンデシルオキシ力ルポニルビニル、２．２−ジドデシル
オキン力ルポニルビニル、２．２−ジトリデシルオキシ
力ルポニルビニル、２，２−ジテトラデシルオキシ力ル
ポニルビニル、２．２−ジペンタデシルオキシ力ルポニ
ルビニルなどのエステル化されていてもよいカルボキシ
ル基を有する２．２ジカルボキシビニル基：２−シアノ
ー２−カルボキシビニル、２−シアノー２−メトキシ力
ルポニルビニル、２−シアノー２−エトキシ力ルポニル
ビニル、２−シアノー２−プロボキシ力ルポニルビニル
、２−シアノー２−イソプロボキシカルボニルビニル、
２−シアノー２−ブトキシ力ルポニルビニル、２−シア
ノー２−イソプトキシカルボニルビニル、２−シアノー
２ − ｔｅｒｔ−ブトキシ力ルポニルビニル、２−シ
アノー２−ペンチルオキシ力ルポニルビニル、２−シア
ノー２−ヘキシルオキシカルポニルビニル、２−シアノ
ー２−へプチルオキシ力ルポニルビニル、２−シアノー
２オクチルオキシ力ルポニルビニル、２−シアノ２−ノ
ニルオキシ力ルポニルビニル、２−シアノー２一デシル
オキシ力ルポニルビニル、２−シアノー２−ウンデシル
オキシ力ルポニルビニル、２−シアノー２−ドデシルオ
キシ力ルポニルビニル、２−シアノー２−トリデシルオ
キシ力ルポニルビニル、２−シアノー２−テトラデシル
オキシ力ルポニルビニル、２−シアノー２−ペンタデシ
ルオキシ力ルポニルビニルなどのエステル化されていて
もよいカルボキシル基を有する２−シアノー２−カルボ
キシビニル基などが例示できる。In the compound represented by general 2m, examples of the electron-withdrawing group , trifluoromethanesulfonyl, 2,2.2
-} Alkanesulfonyl group which may have a halogen atom such as trifluoroethanesulfonyl; Sulfonyl group; methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, isopropoxysulfonyl, butoxysulfonyl, tert-butoxysulfonyl, pentyloxysulfonyl, hexyl Esterified sulfonyl groups such as alkoxysulfonyl such as oxysulfonyl and octyloxysulfonyl, phenoxysulfonyl which may have a substituent such as phenoxysulfonyl and p-cyanophenoxysulfonyl; carboxyl group; methoxy group; carbonyl, ethoxycarbonyl, propoxycarbonyl, isobropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, hebutyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, denoxycarbonyl, Substituents such as alkoxycarbonyl groups such as decyloxycarbonyl, dodecyloxycarbonyl, tridecyloxycarbonyl, tetradecyloxycarbonyl, pentadecyloxycarbonyl, phenoxycarbonyl, p-nitrophenoxycarbonyl, etc. Esterified carboxyl groups such as aralkyloxycarbonyl such as aryloxycarbonyl, penzhydryloxycarbonyl, which may have; acyl groups such as formyl, acetyl, probionyl, butyryl, hexanoyl, benzoyl; Carbamoyl groups which may have substituents such as carbamoyl, methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, probilcarbamoyl, phenylcarbamoyl, benzylcarbamoyl; sulfamoyl, methylsulfamoyl, ethylsulfamoyl, A sulfamoyl group which may have a substituent such as nylsulfamoyl or benzylsulfamoyl; a nitroso group; a sulfino group; a thiocarboxyl group (wherein A represents a cyano group, a carboxyl group or an alkoxycarbonyl group); and R1 represents a hydrogen atom or an alkyl group), for example, 2,2-dicarboxyvinyl, 2
-Carboxy-2-methoxyluponylvinyl, 2-carboxy-2-ethoxyluponylvinyl, 2-carboxy-2-proboxycarponylvinyl, 2-carboxy-2isobropoxycarbonylvinyl, 2,2-dimethoxyluponylvinyl, 2. 2-Ethoxyluponylvinyl, 2 2-diproboxyluponylvinyl, 2.
2-diisopropoxycarbonylvinyl, 2-methoxycarbonyl-2-ethoxycarbonylvinyl, 2-methoxycarbonyl-2-propoxycarponylvinyl, 2
-Ethoxycarbonyl-2-propoxycarbonylvinyl, 2-ethoxycarbonyl-2-isopropoxycarbonylvinyl, 2,2-dibutoxycarbonylvinyl,
2.2-diisobutoxyluponylvinyl, 2.2-di-tert-butoxyluponylvinyl, 2.2-dipentyloxyluponylvinyl. Vinyl, 2,2-dihexyloxycarbonylvinyl, 2,2-diheptyloxycarbonylvinyl, 2,2-dioctyloxycarbonylvinyl, 2,2-dinonyloxyvinylvinyl,
．． 2-Didecyloxyluponylvinyl, 2,2-diundecyloxyluponylvinyl, 2,2-didodecyloxyluponylvinyl, 2,2-ditridecyloxyluponylvinyl, 2,2-ditetradecyloxyluponylvinyl, 2,2-didecyloxyluponylvinyl, 2.2 dicarboxyvinyl group having an optionally esterified carboxyl group such as pentadecyloxylponylvinyl: 2-cyano2-carboxyvinyl, 2-cyano2-methoxylponylvinyl, 2-cyano2-ethoxylvinyl luponyl vinyl, 2-cyano 2-proboxylic luponyl vinyl, 2-cyano 2-isoproboxycarbonyl vinyl,
2-cyano-2-butoxycarbonylvinyl, 2-cyano-2-isoptoxycarbonylvinyl, 2-cyano-2-tert-butoxycarbonylvinyl, 2-cyano-2-pentyloxycarbonylvinyl, 2-cyano-2-hexyloxycarponylvinyl, 2-cyano2-heptyloxyluponylvinyl, 2-cyano2-octyloxyluponylvinyl, 2-cyano2-nonyloxyluponylvinyl, 2-cyano2-decyloxyluponylvinyl, 2-cyano2-undecyloxyluponylvinyl, 2- Carboxyl which may be esterified, such as cyano-2-dodecyloxy-ruponyl vinyl, 2-cyano-2-tridecyloxy-ruponyl vinyl, 2-cyano-2-tetradecyloxy-ruponyl vinyl, 2-cyano-2-pentadecyloxy-ruponyl vinyl, etc. A 2-cyano-2-carboxyvinyl group having a group can be exemplified.
上記置換基Ｘは、所望する電子吸引性の強さや非線形光
学効果などに応じて適宜選択することができるか、これ
らの置換基のなかでは、電子吸引性の強さから、ニトロ
基が好ましい。また、上記置換基Ｘは適宜の位置に置換
しても良いが、大きな永久双極子モーメントを有し、非
線形光学定数数βを大きくする上で前記の複素５員環骨
格の５位に置換しているものが好ましい。The above-mentioned substituent X can be appropriately selected depending on the desired strength of electron-withdrawing property, nonlinear optical effect, etc. Among these substituents, a nitro group is preferable in view of the strength of electron-withdrawing property. Furthermore, the above substituent X may be substituted at an appropriate position, but since it has a large permanent dipole moment, in order to increase the nonlinear optical constant β, it is preferable to substitute it at the 5-position of the above-mentioned five-membered heterocyclic ring skeleton. Preferably.
電子供与性基Ｙとしては、例えば、メチル、エチル、プ
ロビル、イソブロビル、ブチル、ｔｅｒｔ −ブチル、
ペンチル、ヘキシル、ヘブチル、オクチル、ノニル、デ
シル、ウンデシル、ドデシル、トリデシル、テトラデシ
ル、ペンタデシルなどのアルキル基、さらに、これと同
じアルキル基；ヒドロキシル基；メチロール、２−ヒド
ロキシエチル、３−ヒドロキシブロビルなどのヒドロキ
シアルキル基；メトキシ、エトキシ、プロボキシ、イソ
プロポキシ、ブトキシ、イソブトキシ、ｔｅｒｔ−ブト
キシ、ペンチルオキシ、ヘキシルオキシ、ヘプチルオキ
シ、オクチルオキシ、ノニルオキシ、デシルオキシ、ウ
ンデシルオキシ、ドデシルオキシ、トリデシルオキシ、
テトラデシルオキシ、ペンタデシルオキシなどのアルコ
キシル基；メルカブト基．メチルチオ、エチルチオ、プ
ロビルチオ、ブチルチオ、ヘキシルチオなどのアルキル
チオ基；ベンジルチオ、フェニルチオ等の置換基を有し
ていてもよいアラルキルチオまたはアリールチオ基：ア
ミノ、メチルアミノ、エチルアミノ、プロビルアミノ、
イソブロビルアミノ、プチルアミノ、ヘキシルアミノ、
ジメチルアミノ、メチルエチルアミノ、ジエチルアミノ
、ジブロビルアミノ、ジブチルアミノなどのアルキル基
を有していてもよいアミノ基：ベンジルアミノ、ペンズ
ヒドリル、トリチルアミノなどのアラルキルアミノ基；
フエニルアミノ、ジフエニルアミノなどのアリールアミ
ノ基；フッ素、塩素、臭素、ヨウ素などのハロゲン原子
等が置換したフエニル基、上記アルキル基、上記フエニ
ル基の置換基として例示のヒドロキシル基、ヒドロキシ
アルキル基、アルコキシル基、メルカプト基、アルキル
チオ基、置換基を有していてもよいアラルキルチオ基ま
たはアリールチオ基、アルキル基を有していてもよいア
ミノ基、アラルキルアミノ基、アリールアミノ基などが
例示される。これらの電子供与性基Ｙのうち、ヒドロキ
シル基またはアルコキシル基が好ましく、特にヒドロキ
シル基が好ましい。Examples of the electron-donating group Y include methyl, ethyl, probyl, isobrobyl, butyl, tert-butyl,
Alkyl groups such as pentyl, hexyl, hebutyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and the same alkyl groups; hydroxyl groups; methylol, 2-hydroxyethyl, 3-hydroxybrobyl, etc. hydroxyalkyl group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy,
Alkoxyl groups such as tetradecyloxy and pentadecyloxy; merkabuto groups. Alkylthio groups such as methylthio, ethylthio, probylthio, butylthio, hexylthio; aralkylthio or arylthio groups that may have substituents such as benzylthio and phenylthio; amino, methylamino, ethylamino, probylamino,
isobrobylamino, butylamino, hexylamino,
Amino groups that may have an alkyl group such as dimethylamino, methylethylamino, diethylamino, dibrobylamino, and dibutylamino; aralkylamino groups such as benzylamino, penzhydryl, and tritylamino;
Arylamino groups such as phenylamino and diphenylamino; phenyl groups substituted with halogen atoms such as fluorine, chlorine, bromine, and iodine, the above alkyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxyl groups as substituents of the above phenyl groups, Examples include a mercapto group, an alkylthio group, an aralkylthio group or an arylthio group that may have a substituent, an amino group that may have an alkyl group, an aralkylamino group, and an arylamino group. Among these electron-donating groups Y, hydroxyl groups or alkoxyl groups are preferred, and hydroxyl groups are particularly preferred.
上記複素５員環中の、ペテロ原子Ｚとしては、例えば、
酸素原子、窒素原子、硫黄原子、セレン原子、テルル原
子が挙げられるが、特に酸素原子、硫黄原子が好ましい
。As the petero atom Z in the above five-membered hetero ring, for example,
Examples include oxygen atom, nitrogen atom, sulfur atom, selenium atom, and tellurium atom, with oxygen atom and sulfur atom being particularly preferred.
上記一般式（Ｉ）で表される複素５員環化合物は、光な
どの電場により分極が生じる際、電子移動度が大きく、
大きな非線形光学定数βを示し、非線形光学材料として
好ましい分子構造および結晶構造となる。特に、前記一
般式（Ｉ１で表される化合物において、Ｘがニトロ基、
Ｙがヒドロキシル基であり、Ｚが酸素原子または硫黄原
子である化合物、すなわち、５−ニトロ−２−フルアル
ドキシムまたは５−ニトロ−２−チオフエン力ルポック
スアルドキシムが、非線形光学定数が大きいので、非線
形光学材料として好ましい。The five-membered heterocyclic compound represented by the above general formula (I) has high electron mobility when polarized by an electric field such as light,
It exhibits a large nonlinear optical constant β, and has a molecular structure and crystal structure suitable as a nonlinear optical material. In particular, in the compound represented by the general formula (I1), X is a nitro group,
Compounds in which Y is a hydroxyl group and Z is an oxygen atom or a sulfur atom, that is, 5-nitro-2-furaldoxime or 5-nitro-2-thiophene group, have large nonlinear optical constants. , preferred as a nonlinear optical material.
なお、上記一般式（Ｉ）で表される化合物のうち、５−
ニトロ−２−フルアルドキシムは公知の化合物であるが
、非線形光学効果に優れていることは知られていない。In addition, among the compounds represented by the above general formula (I), 5-
Although nitro-2-furaldoxime is a known compound, it is not known to have excellent nonlinear optical effects.
前記一般式（Ｉ１で表される化合物は、種々の方法によ
り合成することができる。例えば、Ｙとしてヒドロキシ
ル基を有する化合物は、下記一般式（Ｉ［）で表される
化合物と下記一般式圓で表される化合物との反応により
合成することができる。The compound represented by the general formula (I1) can be synthesized by various methods. For example, a compound having a hydroxyl group as Y can be synthesized by combining a compound represented by the following general formula (I[) and the following general formula It can be synthesized by reaction with a compound represented by:
（式中、Ｘ，ｚは前記に同じ）
上記一般式（Ｉ［）で表される化合物と一般式ｌで表さ
れる化合物とから前記一般式［Ｉ］で表される化合物を
得る反応は、通常有機溶媒中、ビベリジンなどの塩基性
物質の存在下で行なわれ、溶媒としては、この反応に悪
影響を及ぼさない溶媒であればいずれの溶媒も使用でき
、例えば、ｎ−ヘキサン、ｎ−オクタン、シクロヘキサ
ン等の脂肪族または脂環族炭化水素類、ベンゼン、トル
エン、キシレン等の芳香族炭化水素類、メタノール、エ
タノール、プロパノール等のアルコール類、アセトン、
メチルエチルケトン等のケトン類、ジェチルエーテル、
テトラヒド口フラン、ジオキサン等の二一テル類、アセ
トニトリル、ジメチルホルムアミド、ジメチルスルホキ
シド、ヘキサメチルリン酸トリアミド等が例示される。(In the formula, X and z are the same as above) The reaction to obtain the compound represented by the above general formula [I] from the compound represented by the above general formula (I[) and the compound represented by the general formula l is This reaction is usually carried out in an organic solvent in the presence of a basic substance such as viveridine, and any solvent can be used as long as it does not adversely affect this reaction, such as n-hexane, n-octane, etc. , aliphatic or alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, alcohols such as methanol, ethanol, and propanol, acetone,
Ketones such as methyl ethyl ketone, diethyl ether,
Examples include tetrahydrofuran, dioxane such as dioxane, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and the like.
該反応は、通常室温または加温ないし還流下で行なわれ
、反応は数時間ないし４８時間程度で終了する。反応終
了後、反応生成物を濃縮し、再結晶、溶媒抽出、カラム
クロマトグラフィー等の慣用の手段で容昌に分離精製す
ることができる。The reaction is usually carried out at room temperature or under heating or reflux, and is completed in several hours to about 48 hours. After the reaction is completed, the reaction product can be concentrated and separated and purified using conventional means such as recrystallization, solvent extraction, and column chromatography.
前記一般式（Ｉ１で表される化合物を少なくとも含有す
る有機非線形光学材料は、一般式（Ｉ）で表される化合
物の単一成分結晶であってもよく、一般式（Ｉ１で表さ
れる化合物と、他の非線形光学材料、水素結合可能な置
換基を有する高分子や液晶性高分子との混合物からなる
混合物結晶または混合物固体であってもよい。The organic nonlinear optical material containing at least the compound represented by the general formula (I1) may be a single-component crystal of the compound represented by the general formula (I), It may also be a mixture crystal or a mixture solid consisting of a mixture of and other nonlinear optical materials, polymers or liquid crystalline polymers having substituents capable of hydrogen bonding.
前記一般式（Ｉ）で表される化合物の単一成分結晶は、
結晶状態でも非線形光学定数βが大きく、顕著な２次非
線形光学効果を有する。また、上記混合物結晶または混
合物固体にあっては、結晶における分子配列を制御し、
２次非線形光学効果の大きな有機非線形光学材料とする
ことができる。The single component crystal of the compound represented by the general formula (I) is:
Even in the crystalline state, the nonlinear optical constant β is large, and it has a remarkable second-order nonlinear optical effect. In addition, in the above mixture crystal or mixture solid, controlling the molecular arrangement in the crystal,
An organic nonlinear optical material with a large second-order nonlinear optical effect can be obtained.
上記他の非線形光学材料としては、種々の有機非線形光
学材料が用いられるが、好ましくは非線形光学定数の大
きい材料、例えば、２次の非線形光学定数βか５ Ｘ
１０−３０ｅｓｕ以上の化合物が用いられる。このよう
な有機非線形光学材料としては、分子内に電子吸引性基
と電子供与性基とを有する化合物、例えば、前記ＭＮＡ
の他、１−メトキシ−４−（２−二トロペンジリデンア
ミノ）ベンゼン、１−エトキシ−４−（２−ニトロペン
ジリデンアミノ）ベンゼン、１−プロポキシー４−（２
ニトロペンジリデンアミノ）ベンゼン、１−ブトキシ−
４−（２−ニトロ゛ベンジリデンアミノ）ベンゼン、１
−へキシルオキシ−４−（２−ニトロペンジリデンアミ
ノ）ベンゼン、１−メトキシ−４−（３−ニトロペンジ
リデンアミノ）ベンゼン、１−エトキシ−４−（３−ニ
トロペンジリデンアミノ）ベンゼン、１−プロボキシ−
４−（３二トロペンジリデンアミノ）ベンゼン、１−ブ
トキシ−４−（３−ニトロペンジリデンアミノ）ベンゼ
ン、１−へキシルオキシ−４−（３−ニトロペンジリデ
ンアミノ）ベンゼン、１−メトキシ４−（４−ニトロペ
ンジリデンアミノ）ベンゼン、１−エトキシ−４−（４
−ニトロペンジリデンアミノ）ベンゼン、１−プロボキ
シー４−（４ニトロペンジリデンアミノ）ベンゼン、１
−ブトキシ−４−（４−ニトロペンジリデンアミノ）ベ
ンゼン、１−ベンチルオキシ−４−（４−ニトロペンジ
リデンアミノ）ベンゼン、１−へキシルオキシ−４−（
４−ニトロペンジリデンアミノ）ベンゼン、１−オクチ
ルオキシ−４−（４−ニトロペンジリデンアミノ）ベン
ゼン、１−ノニルオキシ−４・−（４−ニトロペンジリ
デンアミノ）ベンゼン、１−メチル−４−（４−ニトロ
ペンジリデンアミノ）ベンゼン、１−エチル−４−（４
−ニトロペンジリデンアミノ）ベンゼン、１−プロピル
−４−（４−ニトロペンジリデンアミノ）ベンゼン、１
−ブチル−４−（４−ニトロペンジリデンアミノ）ベン
ゼン、１−（４−ニトロペンジリデンアミノ）−４−ヘ
キシルベンゼン、１ー（４−ニトロペンジリデンアミノ
）−４−オクチルベンゼン、１−エチル−４−（４−シ
アノベンジリデンアミノ）ベンゼン等のシッフ塩基型化
合物；１−メチルアミノアントラキノン、２−メチルア
ミノアントラキノン、１．４−ジアミノ−６エトキシ力
ルポニルアントラキノン、１．４−ジアミノー２−（Ｉ
−ピロリジニル）アントラキノン等のアントラキノン誘
導体；エチル １．３−ジチオール−２−イリデンシア
ノアセテート、エチル ４−メチル−１．３−ジチオー
ル−２−イリデンシアノアセテート等のジチオール誘導
体；β．β−ジシアノ−４−メトキシスチレン、β．β
−ジシアノ−４−メチルスチレン、４−ジメチルアミノ
ーβ，β−ジシアノスチレン等のスチレン誘導体；２−
ブロモー４−ニトロ一Ｎ，Ｎ−ジメチルアニリン．４−
Ｎ，Ｎ−ジメチルアミノー４゛一二トロスチルベン；２
−エチルアミノー１，３．４−チアジアゾール．４−（
４’ −ジメチルアミノアニリノ）−２．５．６−｝リ
フルオ口−１．３−ジシアノベンゼン、４−（４’一メ
トキシチオフエノキシ）−２．５．６−｝リフルオ口−
１．３−ジシアノベンゼン等のベンゼン誘導体：３．５
−ジメチル−２’ ，４’ −ジニトロ−１．１′−
ビフエニル−４−オール、３．５−ジーｔｅ『ｔ−ブチ
ルー２’ ，４’−ジニトロ−１．１′ビフエニル−４
−オール等のビフエニル誘導体；３−アミノピリジンな
どが例示される。前記一般式（Ｉ）で表される化合物と
上記の有機非線形光学材料との混合比は、所望する光学
特性、化合物の物性（例えば、融点、溶解度、λｎ＋ａ
ｘなど）等により適宜選択できる。Various organic nonlinear optical materials can be used as the other nonlinear optical material, but preferably a material with a large nonlinear optical constant, such as a second-order nonlinear optical constant β or 5
A compound of 10-30 esu or more is used. Such organic nonlinear optical materials include compounds having an electron-withdrawing group and an electron-donating group in the molecule, such as the above-mentioned MNA.
In addition, 1-methoxy-4-(2-nitropenzylideneamino)benzene, 1-ethoxy-4-(2-nitropenzylideneamino)benzene, 1-propoxy-4-(2-nitropenzylideneamino)benzene,
Nitropenzylideneamino)benzene, 1-butoxy-
4-(2-nitrobenzylideneamino)benzene, 1
-hexyloxy-4-(2-nitropenzylideneamino)benzene, 1-methoxy-4-(3-nitropenzylideneamino)benzene, 1-ethoxy-4-(3-nitropenzylideneamino)benzene, 1- Proboxy
4-(3-nitropenzylideneamino)benzene, 1-butoxy-4-(3-nitropenzylideneamino)benzene, 1-hexyloxy-4-(3-nitropenzylideneamino)benzene, 1-methoxy4- (4-Nitropenzylideneamino)benzene, 1-ethoxy-4-(4
-Nitropenzylideneamino)benzene, 1-proboxy4-(4nitropenzylideneamino)benzene, 1
-Butoxy-4-(4-nitropenzylideneamino)benzene, 1-bentyloxy-4-(4-nitropenzylideneamino)benzene, 1-hexyloxy-4-(
4-Nitropenzylideneamino)benzene, 1-octyloxy-4-(4-nitropenzylideneamino)benzene, 1-nonyloxy-4·-(4-nitropenzylideneamino)benzene, 1-methyl-4-( 4-Nitropenzylideneamino)benzene, 1-ethyl-4-(4
-Nitropenzylideneamino)benzene, 1-propyl-4-(4-nitropenzylideneamino)benzene, 1
-Butyl-4-(4-nitropenzylideneamino)benzene, 1-(4-nitropenzylideneamino)-4-hexylbenzene, 1-(4-nitropenzylideneamino)-4-octylbenzene, 1-ethyl Schiff base type compounds such as -4-(4-cyanobenzylideneamino)benzene; 1-methylaminoanthraquinone, 2-methylaminoanthraquinone, 1.4-diamino-6ethoxyluponylanthraquinone, 1.4-diamino-2- (I
-pyrrolidinyl) anthraquinone; dithiol derivatives such as ethyl 1,3-dithiol-2-ylidene cyanoacetate, ethyl 4-methyl-1,3-dithiol-2-ylidene cyanoacetate; β. β-dicyano-4-methoxystyrene, β. β
- Styrene derivatives such as dicyano-4-methylstyrene, 4-dimethylamino-β,β-dicyanostyrene; 2-
Bromo-4-nitro-N,N-dimethylaniline. 4-
N,N-dimethylamino-4゛12trostilbene; 2
-ethylamino-1,3,4-thiadiazole. 4-(
4'-dimethylaminoanilino)-2.5.6-}refluoro-1.3-dicyanobenzene, 4-(4'-methoxythiophenoxy)-2.5.6-}refluoro-
Benzene derivatives such as 1.3-dicyanobenzene: 3.5
-dimethyl-2',4'-dinitro-1,1'-
Biphenyl-4-ol, 3,5-dite't-butyl-2',4'-dinitro-1,1'biphenyl-4
Biphenyl derivatives such as -ol; 3-aminopyridine and the like are exemplified. The mixing ratio of the compound represented by the general formula (I) and the organic nonlinear optical material is determined based on desired optical properties and physical properties of the compound (e.g., melting point, solubility, λn+a
x, etc.), etc.).
なお、一般式（Ｉ）で表される化合物の単一成分からな
る結晶、または一般式（Ｉ）で表される化合物と前記他
の非線形光学材料との混合物結晶は、例えば、一般式（
Ｉ）で表される化合物などを加熱溶融後、冷却して結晶
化させる方法；適当な溶媒に適当な温度で溶解した後、
溶媒を除去するかまたは温度を降下させることにより、
結晶化させる方法；真空蒸着、分子線エビタキシー等の
気相成長法を用いる方法等で調製できる。なお、第１の
結晶化法においては、結晶化させる際、一般式［１］で
表され化合物の融液を温度勾配を有する加熱炉中で結晶
化させる融液固化法であってもよい。また、第２の結晶
化法で使用される有機溶媒は、水素結合か可能なヒドロ
キシル基を有するメタノール、エタノールなどの極性溶
媒でもよく、アセトニトリル、酢酸エチル、ジエチルエ
ーテル、テトラヒド口フランなどの極性溶媒、ベンゼン
、トルエン、シクロヘキサンなどの無極性または極性の
小さな溶媒であってもよい。なお、この際、必要により
、不斉炭素を有する溶媒、例えば、（Ｒ）−２−ブタノ
ール等の不斉炭素を有する溶媒より結晶を得てもよい。Incidentally, a crystal consisting of a single component of the compound represented by the general formula (I) or a mixture crystal of the compound represented by the general formula (I) and the other nonlinear optical material is, for example, a crystal consisting of a single component of the compound represented by the general formula (I).
A method in which a compound represented by I) is melted by heating and then cooled to crystallize; after dissolving in an appropriate solvent at an appropriate temperature,
By removing the solvent or lowering the temperature,
Crystallization method: It can be prepared by a method using a vapor phase growth method such as vacuum evaporation or molecular beam epitaxy. The first crystallization method may be a melt solidification method in which a melt of the compound represented by the general formula [1] is crystallized in a heating furnace having a temperature gradient. The organic solvent used in the second crystallization method may be a polar solvent such as methanol or ethanol that has a hydroxyl group capable of hydrogen bonding, or a polar solvent such as acetonitrile, ethyl acetate, diethyl ether, or tetrahydrofuran. , benzene, toluene, cyclohexane, and the like. At this time, if necessary, crystals may be obtained from a solvent having an asymmetric carbon, for example, a solvent having an asymmetric carbon such as (R)-2-butanol.
また、上記水素結合可能な置換基を有する高分子として
は、ヒドロキシル基、カルボニル基、カルボキシル基、
エーテル基などの水素結合可能な基を有する高分子、例
えば、ポリビニルアルコール、ポリメチルメタクリレー
ト、ポリアクリレートなどのアクリル樹脂、ポリエチレ
ンオキサイトなどのポリアルキレンオキサイドなどが例
示される。In addition, examples of the polymer having a substituent capable of hydrogen bonding include a hydroxyl group, a carbonyl group, a carboxyl group,
Examples include polymers having groups capable of hydrogen bonding such as ether groups, such as acrylic resins such as polyvinyl alcohol, polymethyl methacrylate, and polyacrylate, and polyalkylene oxides such as polyethylene oxide.
また、上記液晶性高分子としては、側鎖にメソーゲン基
を有する側鎖型液晶性高分子、側鎖型ポリアクリレート
系液晶高分子、側鎖型ポリシロキサン系液晶高分子など
が例示される。Further, examples of the liquid crystal polymer include a side chain type liquid crystal polymer having a mesogen group in a side chain, a side chain type polyacrylate type liquid crystal polymer, and a side chain type polysiloxane type liquid crystal polymer.
前記水素結合可能な置換基を有する高分子や上記液晶性
高分子との混合物固体とすることにより、水素結合可能
な置換基を有する高分子と液晶性高分子の分子配向性を
利用して前記一般式（Ｉ）で表される化合物の分子配列
を制御することができる。By forming a solid mixture of the polymer having a substituent capable of hydrogen bonding and the liquid crystalline polymer, the molecular orientation of the polymer having a substituent capable of hydrogen bonding and the liquid crystalline polymer is utilized to obtain the above. The molecular arrangement of the compound represented by general formula (I) can be controlled.
なお、前記一般式｛１｝で表される化合物のうち、電子
吸引性基Ｘがアルキル部分を有する化合物、特にアルコ
キシ部分の炭素数１〜２０の２．２−ジアルコキシ力ル
ポニルビニル基または２−シアノー２−アルコキシ力ル
ポニルビニル基である化合物は、上記高分子との相溶性
に優れているので、前記混合物固体における一般式（Ｉ
）で表される化合物の分子配列をより一層制御すること
ができる。In addition, among the compounds represented by the general formula {1}, the electron-withdrawing group A compound having a cyano-2-alkoxy group has excellent compatibility with the above-mentioned polymer, so that the compound having the general formula (I) in the solid mixture is
) can further control the molecular arrangement of the compound represented by
また、前記の一般式（Ｉ）で表される化合物と、水素結
合可能な置換基を有する高分子や液晶性高分子との混合
物固体は、一般式（Ｉ］で表される化合物と液晶性高分
子などとの混合物を溶融させた後、徐々に冷却して液晶
状態などとし、次いで電場を印加し、その状態で冷却し
固化させることにより得られる。電場の印加により水素
結合可能な置換基を有する高分子や液晶性高分子が配向
した状態で固化するので、一般式（Ｉ）で表される化合
物が対称中心を持たない分子配列状態の固体を得ること
ができる。上記の一般式（Ｉ）で表される化合物と、水
素結合可能な置換基を有する高分子や液晶性高分子との
混合物において、各成分の混合比は一般式（Ｉ）で表さ
れる化合物か分子配向した固体状聾をとり得るものであ
れば特に限定されず、一般式（Ｉ１で表される化合物お
よび使用される水素結合可能な置換基を有する高分子や
液晶性高分子の性状（例えば、相転移温度など）等によ
り適宜選択することができ、通常一般式（Ｉ）で表され
る化合物の含有量は、２〜６０重量％程度とされる。In addition, a solid mixture of the compound represented by the general formula (I) and a polymer or liquid crystalline polymer having a substituent capable of hydrogen bonding may be a mixture of the compound represented by the general formula (I) and a liquid crystalline polymer. It is obtained by melting a mixture with a polymer, etc., and then gradually cooling it to a liquid crystal state, etc., then applying an electric field, and cooling and solidifying in that state. Substituents that can hydrogen bond by applying an electric field. Since the polymer or liquid crystalline polymer having the above-mentioned general formula ( In a mixture of the compound represented by formula (I) and a polymer or liquid crystalline polymer having a substituent capable of hydrogen bonding, the mixing ratio of each component is between the compound represented by general formula (I) and the molecularly oriented solid. It is not particularly limited as long as it can cause deafness; etc.), and the content of the compound represented by general formula (I) is usually about 2 to 60% by weight.
上記のように、前記一般弐ｍで表される化合物を少なく
とも含有する有機非線形光学材料は、非線形光学定数β
が大きく、顕著な非線形光学効果を有する。従って、オ
プトエレクトロニクス分野で使用される非線形光学素子
用材料、例えば、光波長変換素子用材料や、位相変調素
子、振幅変調素子、周波数変調素子、パルス変調素子、
偏波面変調素子等の光変調素子用材料として好適である
。As mentioned above, the organic nonlinear optical material containing at least the compound represented by the general formula 2 has a nonlinear optical constant β
is large and has significant nonlinear optical effects. Therefore, materials for nonlinear optical elements used in the optoelectronics field, such as materials for optical wavelength conversion elements, phase modulation elements, amplitude modulation elements, frequency modulation elements, pulse modulation elements,
It is suitable as a material for optical modulation elements such as polarization plane modulation elements.
く実施例〉 以下に、実施例に基づいて本発明を詳細に説明する。Example The present invention will be explained in detail below based on examples.
合成例１
５−ニトロ−２−フルアルデヒド０．７１ｇをエタノー
ル５０１１に溶解させたものに、塩酸ヒドロキシルアミ
ン０．３５ｇと酢酸ナトリウム０．５ｇを水３０ν！に
溶解させたものを加えた。Synthesis Example 1 To 0.71 g of 5-nitro-2-furaldehyde dissolved in 5011 ethanol, 0.35 g of hydroxylamine hydrochloride and 0.5 g of sodium acetate were added to 30 ν of water! was added to the solution.
この溶液を２時間加熱還流させた後、溶媒を留去し、沈
澱を得た。該沈澱を濾過し、ベンゼンで再結晶させるこ
とにより５−ニトロ−２−フルアルドキシムを得た。After heating and refluxing this solution for 2 hours, the solvent was distilled off to obtain a precipitate. The precipitate was filtered and recrystallized from benzene to obtain 5-nitro-2-furaldoxime.
融点：１１９〜１２０℃
合成例２
５−ニトロ−２−フルアルデヒドの代わりに、５−ニト
ロ−２−チオフェン力ルボックスアルデヒドを用いたほ
かは、合成例１と同様にして５一ニトロ−２−チオフェ
ン力ルポックスアルドキシムを得た。Melting point: 119-120°C Synthesis Example 2 5-Nitro-2- Thiophene lupoxaldoxime was obtained.
融点＝１６２〜１６３℃
実施例１〜２
合成例１で得た５−ニトロ−２−フルアルドキシム（実
施例１）及び合成例２で得た５−ニトロ−２−チオフエ
ン力ルポックスアルドキシム（実施例２）の各試料粉末
に波長１．０６４μｍのＮｄ ： ＹＡＧレーザ光を照
射したところ、波長０．５３２μ一の第２高調波である
緑色光の発生が目視にて観測され、上記各化合物が２次
の非線形光学効果を有していることが判明した。Melting point = 162 to 163°C Examples 1 to 2 5-nitro-2-furaldoxime obtained in Synthesis Example 1 (Example 1) and 5-nitro-2-thiophene compound obtained in Synthesis Example 2 When each sample powder of (Example 2) was irradiated with Nd:YAG laser light with a wavelength of 1.064 μm, the generation of green light, which is the second harmonic with a wavelength of 0.532 μm, was visually observed. It was found that the compound has a second-order nonlinear optical effect.
く発明の効果〉
以上のように、本発明の有機非線形光学材料によれば、
前記一般式（Ｉ）で表される化合物が、複素５員環骨格
が電子供与性基と電子吸引性基を含む置換基とを有する
ので、前記一般弐ｍで表される化合物を含有する有機非
線形光学材料は、光などの電場により分極が生ずる際の
電子移動が速やかに起こり、非線形光学定数βが大きく
、顕著な非線形光学効果を示す。Effects of the Invention> As described above, according to the organic nonlinear optical material of the present invention,
Since the compound represented by the general formula (I) has a substituent containing an electron-donating group and an electron-withdrawing group in its five-membered heterocyclic ring skeleton, an organic compound containing the compound represented by the general formula (I) In nonlinear optical materials, electron movement occurs quickly when polarization occurs due to an electric field such as light, and the nonlinear optical constant β is large, so that a significant nonlinear optical effect is exhibited.
Claims (1)
含有することを特徴とする有機非 線形光学材料。 ▲数式、化学式、表等があります▼（ I ） （式中、Ｘは電子吸引性基、Ｙは電子供与性基、Ｚはヘ
テロ原子を示す。）[Claims] 1. An organic nonlinear optical material containing at least a compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, X represents an electron-withdrawing group, Y represents an electron-donating group, and Z represents a heteroatom.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5827389A JPH02238443A (en) | 1989-03-11 | 1989-03-11 | Organic nonlinear optical material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5827389A JPH02238443A (en) | 1989-03-11 | 1989-03-11 | Organic nonlinear optical material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02238443A true JPH02238443A (en) | 1990-09-20 |
Family
ID=13079579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5827389A Pending JPH02238443A (en) | 1989-03-11 | 1989-03-11 | Organic nonlinear optical material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02238443A (en) |
-
1989
- 1989-03-11 JP JP5827389A patent/JPH02238443A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2700475B2 (en) | Nonlinear optical materials and elements | |
| JPH02238443A (en) | Organic nonlinear optical material | |
| JPS63261233A (en) | Secondary nonlinear optical material | |
| JPH04202167A (en) | Cyclobutenedione derivative and its production | |
| JP2819826B2 (en) | Cyclobutenedione derivative and method for producing the same | |
| JPH0371117A (en) | Material for nonlinear optical element | |
| JPH0440429A (en) | Nonlinear optical material | |
| JPH0678301B2 (en) | Square lilium derivative and method for producing the same | |
| JP2539850B2 (en) | Nonlinear optical material and nonlinear optical element using the same | |
| JP2539855B2 (en) | Nonlinear optical material and nonlinear optical element using the same | |
| JP2539849B2 (en) | Nonlinear optical material and nonlinear optical element using the same | |
| JPH01101523A (en) | Nonlinear optical material and nonlinear optical element formed by using said material | |
| JPH01205130A (en) | Nonlinear optical material | |
| JP2539834B2 (en) | Non-linear optical element | |
| JPH03122624A (en) | Organic nonlinear optical material | |
| JPH01229235A (en) | Organic nonlinear optical material and nonlinear optical element using same | |
| JP2540584B2 (en) | Second-order nonlinear optical material and nonlinear optical element using the same | |
| JPH01173017A (en) | Organic second order non-linear optical material | |
| JPH04202166A (en) | Cyclobutenedione derivative and its production | |
| JPH04199135A (en) | Nonlinear optical element material | |
| JPH0450930A (en) | Nonlinear optical material | |
| EP0534596A2 (en) | Novel hydrazine compound, process for the preparation of the same, and non-linear optical organic material | |
| JPH0784292A (en) | Organic nonlinear optical material | |
| JPH01229234A (en) | Organic nonlinear optical material and nonlinear optical element using same | |
| JPH02934A (en) | Nonlinear optical material |