WO2001058856A1 - Non-linear optically active compounds - Google Patents
Non-linear optically active compounds Download PDFInfo
- Publication number
- WO2001058856A1 WO2001058856A1 PCT/US2000/017776 US0017776W WO0158856A1 WO 2001058856 A1 WO2001058856 A1 WO 2001058856A1 US 0017776 W US0017776 W US 0017776W WO 0158856 A1 WO0158856 A1 WO 0158856A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- optically active
- nitrophenylazo
- phenoxy
- dimethyl
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005647 linker group Chemical group 0.000 claims abstract description 7
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 6
- -1 poly(vinylcarbazole) Polymers 0.000 claims description 34
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 claims description 5
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000013500 data storage Methods 0.000 claims description 2
- 238000003384 imaging method Methods 0.000 claims description 2
- RNAJZRNZBQCGFX-UHFFFAOYSA-N [4-[12-[2,5-dimethyl-4-[(4-nitrophenyl)diazenyl]phenoxy]dodecoxy]-2,5-dimethylphenyl]-(4-nitrophenyl)diazene Chemical compound CC=1C=C(OCCCCCCCCCCCCOC=2C(=CC(=C(C)C=2)N=NC=2C=CC(=CC=2)[N+]([O-])=O)C)C(C)=CC=1N=NC1=CC=C([N+]([O-])=O)C=C1 RNAJZRNZBQCGFX-UHFFFAOYSA-N 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000001093 holography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ICATXIRRADGWQT-UHFFFAOYSA-N n,n-dimethyl-2-nitro-3-(2-phenylethenyl)aniline Chemical compound CN(C)C1=CC=CC(C=CC=2C=CC=CC=2)=C1[N+]([O-])=O ICATXIRRADGWQT-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- SIBVHGAPHVRHMJ-UHFFFAOYSA-N 1,11-dibromoundecane Chemical compound BrCCCCCCCCCCCBr SIBVHGAPHVRHMJ-UHFFFAOYSA-N 0.000 description 1
- ZJJATABWMGVVRZ-UHFFFAOYSA-N 1,12-dibromododecane Chemical compound BrCCCCCCCCCCCCBr ZJJATABWMGVVRZ-UHFFFAOYSA-N 0.000 description 1
- QLIMAARBRDAYGQ-UHFFFAOYSA-N 1,6-diiodohexane Chemical compound ICCCCCCI QLIMAARBRDAYGQ-UHFFFAOYSA-N 0.000 description 1
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 description 1
- POJAQDYLPYBBPG-UHFFFAOYSA-N 2-(2,4,7-trinitrofluoren-9-ylidene)propanedinitrile Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=C(C#N)C#N)C2=C1 POJAQDYLPYBBPG-UHFFFAOYSA-N 0.000 description 1
- LPNANKDXVBMDKE-UHFFFAOYSA-N 5-bromopent-1-ene Chemical compound BrCCCC=C LPNANKDXVBMDKE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FOQABOMYTOFLPZ-ISLYRVAYSA-N Disperse Red 1 Chemical compound C1=CC(N(CCO)CC)=CC=C1\N=N\C1=CC=C([N+]([O-])=O)C=C1 FOQABOMYTOFLPZ-ISLYRVAYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical class NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 229910014307 bSiO Inorganic materials 0.000 description 1
- DSVRVHYFPPQFTI-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane;platinum Chemical compound [Pt].C[Si](C)(C)O[Si](C)(C=C)C=C DSVRVHYFPPQFTI-UHFFFAOYSA-N 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
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 125000006840 diphenylmethane group Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B43/00—Preparation of azo dyes from other azo compounds
- C09B43/28—Preparation of azo dyes from other azo compounds by etherification of hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/008—Dyes containing a substituent, which contains a silicium atom
-
- 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
- G02F1/3611—Organic materials containing Nitrogen
-
- 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
- G02F1/3615—Organic materials containing polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
- G03H2001/0264—Organic recording material
Definitions
- the invention relates to non-linear optically active compounds and, more specifically, to compounds including at least two azo moieties and their synthesis.
- Non-linear optically active compounds can be used in electrooptical switches and modulators.
- Materials which are non-linear optically active typically consist of molecules in a noncentrosymmetric alignment.
- NLO-active To be NLO-active, a molecule must possess a large molecular second- order hyperpolarizability.
- the most common way to align an NLO-active compound is to expose the material into which the compound is incorporated to an electric field. Any ordering process based on electric field-induced alignment (i.e., poling) requires a large value for the molecular dipole moment.
- the vector product of the hyperpolarizability multiplied by the dipole moment is a measure of the maximum non-linearity that can be achieved by the ordering process.
- an organic molecule typically to have a large vector product, it will generally have a delocalized ⁇ -electron system to which both an electron donor group and an electron acceptor group are coupled.
- DANS Disperse Red 1 and dimethylaminonitrostilbene
- One aspect of the present invention provides a non-linear optically active compound including at least two azo moieties linked by a linking group selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group, preferably a cyclotetrasiloxyl group; wherein the at least two azo moieties have the formula:
- the alkyl group has from 4 to 12 carbon atoms.
- the non-linear optically active compounds of the present invention are selected from the group consisting of l,6-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxyhexane; 1,1 l-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) undecane; l,12-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) dodecane); and l,3,5,7-tetrakis(5'-(2",5"-dimethyI)-4"- (4"'-nitrophenylazo) phenoxy)pentyl-l,3,5,7-tetrarnethylcyclotetrasiloxane.
- the recording media includes (a) a substrate layer; (b) a capping layer; and (c) a photoreactive layer between the substrate layer and the capping layer, the photoreactive layer comprising a non- linear optically active compound comprising at least two azo moieties linked by a linking group selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group; wherein the at least two azo moieties have the formula:
- the photoreactive layer is positioned between two transparent electrodes.
- at least one of the transparent electrodes includes indium tin oxide.
- the photoreactive layer further includes poly(vinylcarbazole) and tetracyano-/ quinone.
- the non-linear optically active compound is selected from the group consisting of l,6-bis(2',5'- dimethyl-4'-(4"-nitrophenylazo)phenoxy) hexane; 1, 1 l-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) undecane; l,12-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) dodecane); l,3,5,7-tetrakis(5'-(2",5"-dimethyl)-4"-(4'"- nitrophenylazo)phenoxy)pentyl- 1,3,5, 7-tetramethylcylcotetrasiloxane, and a combination thereof.
- Figure 1 is a schematic illustration of a holographic medium incorporating a non-linear optically active compound of the present invention.
- a non-linear optically active compound in accordance with the present invention includes at least two azo moieties linked by a linking group, wherein the at least two azo moieties have the formula
- R 1 in each of the at least 2 azo moieties can be the same or different groups
- the linking group is selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group
- a non-linear optically active compound in accordance with the present invention is selected from the group consisting of l ,6-bis(2',5'- d ⁇ methyl-4'-(4"-nitrophenylazo)phenoxyhexane, 1, 1 l-b ⁇ s(2',5'
- a non-linear optically active compound in accordance with the present invention can be prepared by conventional methods utilizing a reactive azo compound
- the reactive azo compound can be prepared by reacting 4-n ⁇ trophenyl diazonium tetrafluoroborate with a phenol
- a non-linear optically active compound according to the present invention having two azo moieties is then formed by reacting the azo compound from above with a halide-containing compound consisting of a hydrocarbon group having at least 2 carbon atoms and two halide atoms.
- a halide-containing compound consisting of a hydrocarbon group having at least 2 carbon atoms and two halide atoms.
- an alkylene dihalide can be used, such as that having the following formula:
- X is a halogen, such as bromine or chlorine, for example, and n 1 can be any integer so long as the alkylene group includes more than 2 carbon atoms.
- n 1 is an integer so that the alkylene group includes more than 4 carbon atoms and, more preferably, from 4 to 12 carbon atoms.
- R 1 is defined as above.
- the reactive azo compound from above can be reacted with an alkenyl halide (e.g., such as CH 2 CH(CH 2 ) 3 Br) to produce a non-linear optically active mono-azo compound
- an alkenyl halide e.g., such as CH 2 CH(CH 2 ) 3 Br
- the mono-azo compound is subsequently hydrosilylated with a polyhydrogenorganosiloxane having the average structural formula selected from the group of.
- each R 3 can be the same or different and independently represents a member selected from the group consisting of monovalent aliphatic and aromatic hydrocarbon groups and halogenated derivatives thereof, cyanoalkyl groups, and a combination thereof, e.g., ethylphenyl, said groups preferably having 1 to 18 carbon atoms
- R represents R " or hydrogen
- y represents a number having a value of 5 to 300
- p represents an integer having a value of 3 to 6 inclusive
- a represents a number having a value of 0 to 2.995, preferably 0.5 to 2
- b represents a number having a value of 0.005 to 2.0
- the sum of a and b is equal to a number having a value from 0.8 to 3.
- a tetra-azo compound made by this procedure has the following formula:
- the present invention also provides unsymmetrical azo-containing nonlinear optically active compounds.
- the following synthesis pathway could be used to form such compounds.
- Non-linear optically active compounds of the present invention may be useful in a variety of applications where liquid crystalline behavior is desired (for use in pigments) and for photorefractive holography, for example.
- a holographic media in photorefractive holography, can be formed that includes a non-linear optically active compound in accordance with the present invention.
- the holographic data recording media 120 comprises a photoreactive layer 122 sandwiched between a substrate layer 121 and capping layer 123
- the photoreactive layer 122 is sandwiched between two electrodes 110 and 112 that are each preferably transparent, such as a layer of indium tin oxide (ITO).
- ITO indium tin oxide
- a substrate layer and a capping layer can be formed from such exemplary materials including, but not limited to, glass, a polymeric material, such as polyvinylchloride, polycarbonate, and the like
- the photoreactive layer includes a mixture of a polymeric photoconductor and a non-linear optically active compound in accordance with the present invention
- the polymeric photoconductors are known in the art and include poly(N-vinylcarbazole) (PVK) as well as other aromatic amines, such as triphenylamine, derivatives of carbazole, and conjugated polymers, such as poly(3- alkylthiophene)s and derivatives of polyphenylenevinylidene Such derivatives are well known in the art
- the polymer backbone may be vinyl, acrylate, or methacrylate
- the polymeric photoconductor is combined with an electron acceptor to form a charge transfer complex
- PVK 2,4,7-trinitro-9-fluorenone
- TNF 2,4,7-trinitro-9-fluorenylidene malononitrile
- a photoreactive layer is preferably sandwiched between two metal-containing, and preferably transparent, layers, such as between two plates of indium tin oxide While not wishing to be bound by any particular theory, it is believed that the metal-containing layers provide a relatively high electric field that is typically required for recording o: 1 a photoreactive holographic medium, as in the present invention, once the medium is exposed to radiation.
- the photoreactive layer optionally includes an amount of a sensitizer effective for enhancing the photosensitivity.
- a sensitizer effective for enhancing the photosensitivity.
- Any of the widely known and readily available sensitizers may be utilized, including specifically, but not exclusively, aryl nitrones, xanthenes, diphenylmethanes, acridines, methines, polymethines, thiazoles, thiazines, azines, aminoketones, porphyrins, colored aromatic polycyclic hydrocarbons, p-substituted aminostyryl compounds, amino methanes, anthraquinones, merocyanines, and squarylium compounds.
- a composition including the non-linear optically active compound of the present invention may be conveniently produced by simply blending together a polymer, a non-linear optically active compound described above, and sensitizer in any desired order. Prior to casting, the composition should be dried to remove any residual solvent because it is believed the presence of any solvent tends to interfere with performance of the holographic data recording media 120.
- the photoreactive composition is positioned (e.g., cast or coated) between a substrate layer 121 and a capping layer 123 to form an intermediate photopreactive layer 122.
- the photoreactive layer 122 can have a thickness of between about 0.1 and 5 mm.
Abstract
A non-linear optically active compound, including at least two azo moieties linked by a linking group selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group; wherein the at least two azo moieties have the formula (I) wherein each R1 can be the same or different and is independently selected from the group consisting of -NO¿2?, -C1,-C(CN)=C(CN)2, -SO3R, and -COOR?2¿, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms, can be used in a variety of applications, including holographic recording media.
Description
NON-LINEAR OPTICALLY ACTIVE COMPOUNDS
FIELD OF THE INVENTION The invention relates to non-linear optically active compounds and, more specifically, to compounds including at least two azo moieties and their synthesis.
BACKGROUND
Non-linear optically active compounds can be used in electrooptical switches and modulators. Materials which are non-linear optically active (NLO- active) typically consist of molecules in a noncentrosymmetric alignment.
To be NLO-active, a molecule must possess a large molecular second- order hyperpolarizability. The most common way to align an NLO-active compound is to expose the material into which the compound is incorporated to an electric field. Any ordering process based on electric field-induced alignment (i.e., poling) requires a large value for the molecular dipole moment. The vector product of the hyperpolarizability multiplied by the dipole moment is a measure of the maximum non-linearity that can be achieved by the ordering process.
Typically, for an organic molecule to have a large vector product, it will generally have a delocalized π-electron system to which both an electron donor group and an electron acceptor group are coupled. Two known molecules possessing these characteristics are Disperse Red 1 and dimethylaminonitrostilbene (DANS).
These, as well as other conventional molecules, are typically incorporated as a side chain group in a linear polymer. One limitation of this type of arrangement is that the noncentrosymmetric alignment necessary for optical nonlinearity, induced by the application of an electric field, tends to relax over time at ambient or slightly elevated temperatures. This, then, results in a lowering or loss of NLO activity. In addressing the stability problem, cross-linked polymers have been utilized in combination with NLO-active compounds. In one system, the polymer cross-links around an NLO-active unit that is attached to the polymer chain at a single point. It is believed that this attachment restricts the free volume available
for the relaxation of the NLO-active moiety. In another system, the polymers are cross-linked through the NLO-active units themselves, in which the NLO-active compound is covalently bound to the polymer chain at more than one point.
SUMMARY OF THE INVENTION
What is yet desired is a non-linear optically active compound that may possess a greater degree of alignment when exposed to an electric field.
One aspect of the present invention provides a non-linear optically active compound including at least two azo moieties linked by a linking group selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group, preferably a cyclotetrasiloxyl group; wherein the at least two azo moieties have the formula:
wherein each R1 can be the same or different and is independently selected from the group consisting of -NO2, -Cl, -C(CN)=C(CN)2, -SO3R, and -COOR2, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms. Preferably, the alkyl group has from 4 to 12 carbon atoms.
Preferably, the non-linear optically active compounds of the present invention are selected from the group consisting of l,6-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxyhexane; 1,1 l-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) undecane; l,12-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) dodecane); and l,3,5,7-tetrakis(5'-(2",5"-dimethyI)-4"- (4"'-nitrophenylazo) phenoxy)pentyl-l,3,5,7-tetrarnethylcyclotetrasiloxane.
Another aspect of the present invention provides a recording media for holographic imaging and data storage. Preferably, the recording media includes (a) a substrate layer; (b) a capping layer; and (c) a photoreactive layer between the substrate layer and the capping layer, the photoreactive layer comprising a non-
linear optically active compound comprising at least two azo moieties linked by a linking group selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group; wherein the at least two azo moieties have the formula:
wherein each R1 can be the same or different and is independently selected from the group consisting of -NO2, -Cl, -C(CN)=C(CN)2, -SO3R, and -COO R2, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms.
Preferably, the photoreactive layer is positioned between two transparent electrodes. In one embodiment, at least one of the transparent electrodes includes indium tin oxide. Preferably, the photoreactive layer further includes poly(vinylcarbazole) and tetracyano-/ quinone. Preferably, the non-linear optically active compound is selected from the group consisting of l,6-bis(2',5'- dimethyl-4'-(4"-nitrophenylazo)phenoxy) hexane; 1, 1 l-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) undecane; l,12-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) dodecane); l,3,5,7-tetrakis(5'-(2",5"-dimethyl)-4"-(4'"- nitrophenylazo)phenoxy)pentyl- 1,3,5, 7-tetramethylcylcotetrasiloxane, and a combination thereof.
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 is a schematic illustration of a holographic medium incorporating a non-linear optically active compound of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides non-linear optically active compounds Preferably, a non-linear optically active compound in accordance with the present invention includes at least two azo moieties linked by a linking group, wherein the at least two azo moieties have the formula
wherein R1 in each of the at least two azo moieties is independently selected from the group consisting of -NO2, -Cl, -C(CN)=C(CN)2, -SO3R, and -COOR2, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms Thus, it is contemplated by the present invention that R1 in each of the at least 2 azo moieties can be the same or different groups Preferably, the linking group is selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group More preferably, a non-linear optically active compound in accordance with the present invention is selected from the group consisting of l ,6-bis(2',5'- dιmethyl-4'-(4"-nitrophenylazo)phenoxyhexane, 1, 1 l-bιs(2',5'-dιmethyl-4'-(4"- nιtrophenylazo)phenoxy) undecane, l,12-bιs(2',5'-dιmethyl-4'-(4"- nιtrophenylazo)phenoxy) dodecane), and l,3,5,7-tetrakιs(5'-(2",5"-dιmethyl)-4"- (4 '"-nitrophenylazo) phenoxy)pentyl- 1,3,5, 7-tetramethylcyclotetrasιloxane
A non-linear optically active compound in accordance with the present invention can be prepared by conventional methods utilizing a reactive azo compound For example, the reactive azo compound can be prepared by reacting 4-nιtrophenyl diazonium tetrafluoroborate with a phenol
to form a reactive azo compound having the formula:
One with skill in the art will appreciate that the -NO2 moiety can be substituted with a moiety selected from the group consisting of -Cl, -C(CN)=C(CN)2, -SO3R, and -COOR2, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms.
A non-linear optically active compound according to the present invention having two azo moieties is then formed by reacting the azo compound from above with a halide-containing compound consisting of a hydrocarbon group having at least 2 carbon atoms and two halide atoms. For example, an alkylene dihalide can be used, such as that having the following formula:
X-eCH X
wherein X is a halogen, such as bromine or chlorine, for example, and n1 can be any integer so long as the alkylene group includes more than 2 carbon atoms. Preferably, n1 is an integer so that the alkylene group includes more than 4 carbon atoms and, more preferably, from 4 to 12 carbon atoms. Utilizing the alkylene
dihalide from above, a resulting non-linear optically active di-azo compound in accordance with the present invention then has the following formula:
Z-iCUϊLT Z
wherein the Z is represented by:
In an alternative embodiment, the reactive azo compound from above can be reacted with an alkenyl halide (e.g., such as CH2CH(CH2)3Br) to produce a non-linear optically active mono-azo compound To form a non-linear optically active poly-azo compound, the mono-azo compound is subsequently hydrosilylated with a polyhydrogenorganosiloxane having the average structural formula selected from the group of.
R3
H or
iφ- IbSiO 4-a-b 2
wherein each R3 can be the same or different and independently represents a member selected from the group consisting of monovalent aliphatic and aromatic hydrocarbon groups and halogenated derivatives thereof, cyanoalkyl groups, and a combination thereof, e.g., ethylphenyl, said groups preferably having 1 to 18 carbon atoms, R represents R" or hydrogen, y represents a number having a value
of 5 to 300, p represents an integer having a value of 3 to 6 inclusive, a represents a number having a value of 0 to 2.995, preferably 0.5 to 2, b represents a number having a value of 0.005 to 2.0, and the sum of a and b is equal to a number having a value from 0.8 to 3. For example, a tetra-azo compound made by this procedure has the following formula:
wherein each R1 can be the same or different and is independently selected from the group consisting of -NO2, -Cl, -C(CN)=C(CN)2, -SO3R, and -COOR2, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms, and wherein n3 is an integer 3 or more.
The present invention also provides unsymmetrical azo-containing nonlinear optically active compounds. For example, the following synthesis pathway could be used to form such compounds.
Non-linear optically active compounds of the present invention may be useful in a variety of applications where liquid crystalline behavior is desired (for use in pigments) and for photorefractive holography, for example.
In photorefractive holography, a holographic media can be formed that includes a non-linear optically active compound in accordance with the present invention. Referring generally to Figure 1, the holographic data recording media 120 comprises a photoreactive layer 122 sandwiched between a substrate layer
121 and capping layer 123 Preferably, the photoreactive layer 122 is sandwiched between two electrodes 110 and 112 that are each preferably transparent, such as a layer of indium tin oxide (ITO).
Materials suitable for use as the substrate layer 121 and capping layer 123 of the holographic data recording media 120 are well known and commercially available from a number of sources Substantially any material having the necessary structural integrity may be employed so long as the material is transparent to the type of electromagnetic radiation to which the photoreactive material 122 is sensitive A substrate layer and a capping layer can be formed from such exemplary materials including, but not limited to, glass, a polymeric material, such as polyvinylchloride, polycarbonate, and the like
Preferably, the photoreactive layer includes a mixture of a polymeric photoconductor and a non-linear optically active compound in accordance with the present invention The polymeric photoconductors are known in the art and include poly(N-vinylcarbazole) (PVK) as well as other aromatic amines, such as triphenylamine, derivatives of carbazole, and conjugated polymers, such as poly(3- alkylthiophene)s and derivatives of polyphenylenevinylidene Such derivatives are well known in the art In the case of triphenylamine and carbazoles, the polymer backbone may be vinyl, acrylate, or methacrylate Preferably, the polymeric photoconductor is combined with an electron acceptor to form a charge transfer complex For example, when PVK is used as the polymeric photoconductor, it can be combined with 2,4,7-trinitro-9-fluorenone (TNF), 2,4,7-trinitro-9-fluorenylidene malononitrile or tetracyanoquinodimethane (TCNQ), for example Alternatively, it may be necessary to form the charge transfer complex by incorporating an independent photosensitizer, such as a fullerene
Preferably, in addition to a substrate layer and a capping layer, a photoreactive layer is preferably sandwiched between two metal-containing, and preferably transparent, layers, such as between two plates of indium tin oxide While not wishing to be bound by any particular theory, it is believed that the metal-containing layers provide a relatively high electric field that is typically
required for recording o: 1 a photoreactive holographic medium, as in the present invention, once the medium is exposed to radiation.
The photoreactive layer optionally includes an amount of a sensitizer effective for enhancing the photosensitivity. Any of the widely known and readily available sensitizers may be utilized, including specifically, but not exclusively, aryl nitrones, xanthenes, diphenylmethanes, acridines, methines, polymethines, thiazoles, thiazines, azines, aminoketones, porphyrins, colored aromatic polycyclic hydrocarbons, p-substituted aminostyryl compounds, amino methanes, anthraquinones, merocyanines, and squarylium compounds. A composition including the non-linear optically active compound of the present invention may be conveniently produced by simply blending together a polymer, a non-linear optically active compound described above, and sensitizer in any desired order. Prior to casting, the composition should be dried to remove any residual solvent because it is believed the presence of any solvent tends to interfere with performance of the holographic data recording media 120.
The photoreactive composition is positioned (e.g., cast or coated) between a substrate layer 121 and a capping layer 123 to form an intermediate photopreactive layer 122. The photoreactive layer 122 can have a thickness of between about 0.1 and 5 mm.
EXAMPLES
The following examples are illustrative of specific embodiments and/or methods according to the present invention. A wide variety of variations from the following examples are within the scope of the present invention and are only to be limited by the appended claims. Unless otherwise noted, all chemicals were commercially available from Aldrich Chemical Co., Milwaukee, WI.
Preparation of the Starting Azo Compound (2,5-dimethyl-4-hydroxy- (4'-nitrophenyl) azobenzene) A suspension of the phenol in water (12.9 g in 150 ml) was treated with a small amount of ION sodium hydroxide to solubilize the phenol. This was then treated with a solution of the diazonium salt in water (25 g in 100 ml). The
mixture was stirred at room temperature for 0.5 hours. A purple solution resulted that was then acidified to give a heavy orange precipitate. This precipitate was filtered and air dried overnight, then dried in vacuo for 16 hours to yield 27.22 g of a brownish solid. UN/Vis 394 (2.70E4). Yield was 95%. This azo compound was then utilized in each of the synthesis below.
Preparation of l,6-bis(2',5'-dimethyI-4'-(4"- nitrophenylazo)phenoxy)hexane
The azo compound from above (3.6 g), 1,6-diiodohexane (2.24 g), and potassium carbonate (2.01 g) were heated at reflux in AR acetone (120 ml) under nitrogen for 36 hours. After 36 hours, TLC (thin layer chromatography) showed no starting material. The mixture was then allowed to cool to room temperature and was then filtered. The filtrate was evaporated and then triturated. A yellow solid was filtered and air dried to yield 2.8 g of a yellow/orange solid. Yield was 67%.
Preparation of l,ll-bis(2',5'-dimethγI-4'-(4"- nitrophcnylazo)phenoxy) undccane
The azo compound from above (3.6 g), 1, 11-dibromoundecane (2.08 g), and sodium carbonate (2.01 g) were heated at reflux in AR acetone (120 ml) under nitrogen for 36 hours. The mixture was allowed to cool to room temperature and then filtered. The filtrate was evaporated and then added to chloroform. The filtrate was then washed with water, filtered, and evaporated to give a 4.0 g of a yellow oil. ΝMR analysis showed a mixture of mono and dialkylated material, starting azo compound, and alkyl bromide. The oil was flash chromatographed in petroleum ether: dichloromethane (3: 1) to give 1.0 g of monoalkylated material. The eluent was increased to 2: 1 petroleum ether:dichloromethane to yield 2.7 g of the desired product. Yield was 59%.
Preparation of l,12-bis(2\5'-dimethy]-4'-(4"- nitrophenylazo)phenoxy) dodecane)
The azo compound from above (3.6 g), 1, 12-dibromododecane (2.17 g), and sodium carbonate (1.44 g) were heated at reflux in AR acetone (120 ml) under nitrogen for 36 hours. After 36 hours, TLC showed a significant amount of starting material. Sodium iodide (1 g) was added and heating at reflux continued for 6 days. The mixture was allowed to cool to room temperature and then filtered. The cake from the filtration was partitioned between chloroform and 2N HC1. The organics were dried, filtered, and evaporated to yield 4.1 g of a yellow solid. The solid was flash chromatographed in chloroform to yield 2.8 g of a yellow solid. Yield was 61%.
Preparation of 2,5-dimethyl(4"-nitrophenyl)-4-(4'-penten-l-yIoxγ) azobenzene
The azo compound from above (15.1 g), 5-bromo-l-pentene (9.1 g), and potassium carbonate (16.9 g) were heated at reflux in AR acetone (250 ml) under nitrogen for 40 hours. After 40 hours, TLC showed no starting azo compound remaining and the reaction color had turned yellow. The mixture was then cooled to room temperature and the solvent was removed in vacuo. The residue was partitioned between chloroform and water. The organics were separated, dried, filtered, and evaporated to yield 18 g of a yellow solid. The solid appeared to be contaminated with the starting bromide. The mixture was then chromatographed in petroleum ether: dichloromethane (3: 1) to yield 16.1 g of a yellow azo compound. Yield was 85%.
Preparation of l,3,5,7-tetrakis(5'-(2",5"-dimethyI)-4"-(4'"- nitrophenylazo) phenoxγ)pentyl-l,3,5,7-tetramethγIcycIotetrasiIoxane
An alkene having the formula: CH2CH(CH2)3-O-azo compound from above was utilized in this synthesis. 2.5 g of the alkene in toluene (50 ml) under nitrogen was treated with 1,3,5,7-tetramethylcyclotetrasiloxane (0.43 g) and the catalyst platinum divinyl tetramethyldisiloxane (2 drops) was added. This mixture was then heated to 60°C. After 50 min., TLC showed that little or no change had
occurred. An additional 5 drops of the catalyst was added to the mixture. TLC showed that only a small amount of the starting alkene remained after another hour, but the reaction was allowed to stir at 60°C overnight. Then the mixture was allowed to cool to room temperature, filtered through a plug of silica gel and washed through with a mixture of 5% ethanol in chloroform. The filtrate was evaporated to yield 2.6 g of a yellow solid. NMR showed a trace of the starting alkene. Chromatography (petroleum ether: chloroform at 1 : 1) separated the alkene to yield 1.9 g of the desired material. Yield was 66%.
All patents, patent applications, and publications disclosed herein are incorporated by reference in their entirety, as if individually incorporated. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the details shown and described, for variations obvious to one skilled in the art will be included within the invention defined by the claims.
Claims
1. A non-linear optically active compound comprising at least two azo moieties linked by a linking group selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group; wherein the at least two azo moieties have the formula:
wherein each R1 can be the same or different and is independently selected from the group consisting of -NO2, -Cl, -C(CN)=C(CN)2, -SO3R, and -COOR2, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms.
2. The non-linear optically active compound of claim 1 , wherein the hydrocarbon group has from 4 to 12 carbon atoms.
3. The non-linear optically active compound of claim 1 , wherein the cyclosiloxyl group is a cyclotetrasiloxyl group.
4. The non-linear optically active compound of claim 1 selected from the group consisting of l,6-bis(2',5'-dimethyl-4'-(4"-nitrophenylazo)phenoxy) hexane; l, l l-bis(2',5'-dimethyl-4'-(4"-nitrophenylazo)phenoxy) undecane; 1,12- bis(2',5'-dimethyl-4'-(4"-nitrophenylazo)phenoxy) dodecane); and 1,3,5,7- tetrakis(5'-(2",5"-dimethyl)-4"-(4'"-nitrophenylazo)phenoxy)pentyl-l,3,5,7- tetramethylcylcotetrasiloxane.
5. A recording media for holographic imaging and data storage, comprising:
(a) a substrate layer;
(b) a capping layer; and (c) a photoreactive layer between the substrate layer and the capping layer, the photoreactive layer comprising a non-linear optically active compound comprising at least two azo moieties linked by a linking group selected from the group consisting of a hydrocarbon group having at least 2 carbon atoms, a linear siloxyl group, and a cyclosiloxyl group; wherein the at least two azo moieties have the formula:
wherein each R1 can be the same or different and is independently selected from the group consisting of -NO2, -Cl, -C(CN)=C(CN)2, -SO3R, and -COOR2, wherein R and R2 are independently selected from the group of hydrogen and an alkyl group having from 1 to 6 carbon atoms.
6. The recording media of claim 5, wherein the photoreactive layer is positioned between two transparent electrodes.
7. The recording media of claim 6, wherein at least one of the transparent electrodes comprises indium tin oxide.
8. The recording media of claim 5, wherein the photoreactive layer further includes poly(vinylcarbazole) and tetracyano-/?-quinone.
9. The recording media of claim 5, wherein the non-linear optically active compound is selected from the group consisting of l ,6-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) hexane; l,l l-bis(2',5'-dimethyl-4'-(4"- nitrophenylazo)phenoxy) undecane; 1 , 12-bis(2 ' , 5 '-dimethyl-4 ' -(4"- nitrophenylazo)phenoxy) dodecane); l,3,5,7-tetrakis(5'-(2",5"-dimethyl)-4"-(4"'- nitrophenylazo)phenoxy)pentyl- 1,3,5, 7-tetramethylcylcotetrasiloxane, and a combination thereof.
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| WO2002033005A3 (en) * | 2000-10-19 | 2003-09-25 | Trans Photonics L L C | Novel substituted-polyaryl chromophoric compounds |
| WO2005066949A1 (en) * | 2003-12-19 | 2005-07-21 | General Electric Company (A New York Corporation) | Novel optical storage materials based on narrowband optical properties |
| CN1918643B (en) * | 2003-12-19 | 2013-03-13 | 通用电气公司 | Novel optical storage materials based on narrowband optical properties |
| JP2009511638A (en) * | 2005-10-18 | 2009-03-19 | ディーシーイー アプリリス，インコーポレイテッド | Photopolymerizable media containing siloxane compounds that support cationic polymerization for holographic storage |
| US8715887B2 (en) | 2010-07-30 | 2014-05-06 | Sabic Innovative Plastics Ip B.V. | Complex holograms, method of making and using complex holograms |
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