CN109293643A - A kind of organic second order non-linear optical chromophore and its preparation method and application of flexible isolating base group modification - Google Patents
A kind of organic second order non-linear optical chromophore and its preparation method and application of flexible isolating base group modification Download PDFInfo
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- CN109293643A CN109293643A CN201710606869.4A CN201710606869A CN109293643A CN 109293643 A CN109293643 A CN 109293643A CN 201710606869 A CN201710606869 A CN 201710606869A CN 109293643 A CN109293643 A CN 109293643A
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- 230000003287 optical effect Effects 0.000 title claims abstract description 64
- 238000012986 modification Methods 0.000 title claims abstract description 30
- 230000004048 modification Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 48
- 229910000077 silane Inorganic materials 0.000 claims abstract description 27
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 73
- 150000001875 compounds Chemical class 0.000 claims description 63
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 239000002274 desiccant Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 229920000515 polycarbonate Polymers 0.000 claims description 8
- 239000004417 polycarbonate Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 7
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical group C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 5
- 229940094989 trimethylsilane Drugs 0.000 claims description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000011161 development Methods 0.000 claims description 3
- 150000002240 furans Chemical class 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- -1 tert-butyl hexichol Chemical compound 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 2
- 239000000284 extract Substances 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
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- 230000015572 biosynthetic process Effects 0.000 description 9
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- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
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- 239000000376 reactant Substances 0.000 description 4
- KTQKOGBTMNDCFG-UHFFFAOYSA-N tert-butyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C(C)(C)C)C1=CC=CC=C1 KTQKOGBTMNDCFG-UHFFFAOYSA-N 0.000 description 4
- 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 4
- YEEBDPWOWRMOBB-UHFFFAOYSA-N 3h-furan-2,2,3-tricarbonitrile Chemical compound N#CC1C=COC1(C#N)C#N YEEBDPWOWRMOBB-UHFFFAOYSA-N 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
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- 229910010272 inorganic material Inorganic materials 0.000 description 3
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- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- BNDRWEVUODOUDW-UHFFFAOYSA-N 3-Hydroxy-3-methylbutan-2-one Chemical compound CC(=O)C(C)(C)O BNDRWEVUODOUDW-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000005102 attenuated total reflection Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
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- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009659 non-destructive testing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 241000238370 Sepia Species 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960005083 chloralodol Drugs 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- 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 Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonlinear Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of organic second order non-linear optical chromophores of flexible isolating base group modification, have a structure thatWherein, R1For the alkyl of C1~C20, the hydroxyalkyl of C1~C10, the hydroxyalkyl of the C1~C10 protected by halogen atom or by the hydroxyalkyl of C1~C10 of protected silane；R2For methyl or trifluoromethyl；R3For the alkyl or phenyl of C1~C20.Electron donor, conjugated pi electron bridge and electron acceptor of the invention can increase intermolecular steric hindrance after combining very well, inhibit the accumulation generated between chromophore molecule by dipole-dipole interaction, intramolecular electron transport ability is improved, conversion of the First-order Molecular Hyperpolarizability of chromophore molecule to material macroscopic view electro-optic coefficient is effectively improved.
Description
Technical field
The present invention relates to organic second-order non-linear optical field of material technology.More particularly, to a kind of flexible isolating base
The organic second order non-linear optical chromophore and its preparation method and application of group's modification.
Background technique
With the fast development of information age, so that the requirement at this stage to communication information material is higher and higher.Due to light
Electronic technology can greatly improve communication efficiency using electric light and photoelectric conversion and all-optical network, to meet information world
Construction and fiber to the home projected demand, therefore in recent decades nonlinear optical material attract always people research it is emerging
Interest is applied to the practical field such as optic communication, photoelectronics and optical information processing.
Integrated optics system has small in volume and more embodies the advantage of photon transmission, believes in optic communication, light
The high-tech sectors such as breath processing, optical sensing, automatic control, electronic countermeasure, photon confrontation, photonic computer have widely
Using.And integrated photosystem includes the important devices such as waveguide fiber, photoswitch, photoconverter, wherein critical light is converted
Device is fabricated by nonlinear optics (NLO) material.
Current commercialized second-order non-linear optical materials are based on inorganic material, but there are electric light for inorganic material
The defects of coefficient is small, and corresponding time is long, to limit its extensive use.Compare inorganic material, nonlinear optical organic material
Material has super fast response speed (subpicosecond even picosecond), low-k, high light injury threshold (GW/cm2Magnitude), it is processable
Performance is good, relatively large nonlinear optical response (1~2 order of magnitude usually higher than mineral crystal) and easy processing processing etc. are excellent
Point, therefore have been to be concerned by more and more people.In order to reach practical requirement, these organic materials will not only have big non-thread
Property optic response, and to meet requirement of the device to its transparency, stability and machinability etc. simultaneously.Due to having
The nonlinear optical response of machine material depends on the nonlinear optical properties of wherein chromophore molecule, so design synthesis has both greatly
Electro-optic coefficient (i.e. the single order molecular hyperpolarizability (β) of micro molecule level and the electro-optic coefficient (r of macroscopic material33)) and it is good
The good transparency, the second-order nonlinear optical chromophore molecule of stability be always for a long time most challenging project it
One.
Although the chromophore at present about the related work of second-order nonlinear optical chromophore, in these work
With very high non-linearity optical coefficient and few.At present it has been reported that these chromophories there is biggish point in the polymer
Interaction force between son causes molecule to be easy aggregation, is converted to macroscopic view so as to cause microcosmic single order molecular hyperpolarizability (β)
Electro-optic coefficient (the r of material33) efficiency it is relatively low, electro-optic coefficient is smaller, is not able to satisfy the requirement of device.
Therefore, the present invention provides a kind of organic second order non-linear optical chromophores of flexible isolating base group modification.
Summary of the invention
It is an object of the present invention to provide a kind of organic second-order non-linear optical color developments of flexible isolating base group modification
Group.The organic second order non-linear optical chromophore steric hindrance of flexible isolating base group modification in the present invention is larger, is not easy to accumulate, dissolve
Property it is good, stability is good, with it is polymer-doped after good film-forming property, be easy to polarize, microcosmic First-order Molecular Hyperpolarizability is to macroscopical electric light system
Number high conversion efficiency is easy to device
It is another object of the present invention to provide a kind of organic second-order non-linear optical of flexible isolating base group modification hairs
The preparation method of color group.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of organic second order non-linear optical chromophore of flexible isolating base group modification has the structure as shown in general formula I:
Wherein, R1For alkyl, hydroxyalkyl, by the hydroxyalkyl of halogen atom protection or by the hydroxyalkyl of protected silane；It is preferred that
Ground, R1For alkyl, hydroxyalkyl or by the hydroxyalkyl of protected silane；
R2For methyl or trifluoromethyl；
R3For alkyl or phenyl.
According to the preferred embodiment of the present invention, the alkyl is the alkyl of C1~C20；Further, of the invention
In certain specific embodiments, for example, alkyl is preferably the alkyl of C1~C15, C1~C10, C1~C5；It is highly preferred that alkyl
For the alkyl of C5~C20, C10~C20, C15~C20.
According to the preferred embodiment of the present invention, the hydroxyalkyl is the hydroxyalkyl of C1~C10；Further, in this hair
In bright certain specific embodiments, for example, hydroxyalkyl is preferably the hydroxyalkyl of C1~C8, C1~C5, C1~C3；More preferably
Ground, hydroxyalkyl are the hydroxyalkyl of C3~C10, C5~C10, C8~C10.
According to the preferred embodiment of the present invention, the hydroxyalkyl protected by halogen atom is to be protected by halogen atom
The hydroxyalkyl of C1~C10；Further, in certain specific embodiments of the invention, for example, the hydroxyl protected by halogen atom
Alkyl is preferably the C1~C8 protected by halogen atom, the hydroxyalkyl of C1~C5, C1~C3；It is highly preferred that being protected by halogen atom
The hydroxyalkyl of shield is the C3~C10 protected by halogen atom, the hydroxyalkyl of C5~C10, C8~C10.
According to the preferred embodiment of the present invention, the hydroxyalkyl by protected silane is by C1~C10 of protected silane
Hydroxyalkyl；Further, in certain specific embodiments of the invention, for example, being preferably by the hydroxyalkyl of protected silane
By the hydroxyalkyl of C1~C8 of protected silane, C1~C5, C1~C3；It is highly preferred that being by silane by the hydroxyalkyl of protected silane
The hydroxyalkyl of C3~C10 of protection, C5~C10, C8~C10.
According to the preferred embodiment of the present invention, the silane in the hydroxyalkyl by protected silane be trimethyl silane,
T-butyldimethyl silane, t-butyl diphenylsilane or dimethylphenylsilaneand.
Chromophore in the present invention is using the triphenylamine and its derivative that flexible isolating group is modification as donor, with thiophene
Ring or ring polyenes structure are conjugated electrons bridge, with tricyano-dihydrofuran (TCF) or three fluorine-substituted tricyano-dihydrofurans
(CF3- TCF) it is that electron acceptor has having for D- π-A structure (D being electron donor, and π is conjugated electrons bridge, and A is electron acceptor)
Machine second-order nonlinear optical chromophore, such chromophore have biggish steric hindrance, are not easy to accumulate, dissolubility is good, stability is good, with
It is polymer-doped after good film-forming property, be easy to polarize, microcosmic First-order Molecular Hyperpolarizability to macroscopical electro-optic coefficient high conversion efficiency, be easy to
The advantages of device.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of the organic second order non-linear optical chromophore of flexible isolating base group modification, including walk as follows
It is rapid:
I) in anhydrous n,N-Dimethylformamide, Compounds of formula II, R0- X and Carbon Dioxide nak response, collection obtain
Compound of formula III；
Wherein R0X is halogen atom, R in-X0For the alkyl of C1~C20 or the hydroxyalkyl of C1~C10；General formula II is as follows:
General formula III is as follows:
Wherein R1For alkyl, hydroxyalkyl, by the hydroxyalkyl of halogen atom protection or by the hydroxyalkyl of protected silane；It is preferred that
Ground, R1For alkyl, hydroxyalkyl or by the hydroxyalkyl of protected silane；Silane in the hydroxyalkyl by protected silane is trimethyl
Silane, t-butyldimethyl silane, t-butyl diphenylsilane or dimethylphenylsilaneand.Formula of III compound of the present invention
Branch with oxygen atom connection has certain electron performance, while can be improved the solubility property of the compound.
Ii compound of formula III, thenyl triphenylphosphine and the Cymag for) obtaining step i), in anhydrous ether
Reaction, collection obtain compound of Formula IV, and formula of IV is as follows
Wherein R1For alkyl, hydroxyalkyl, by the hydroxyalkyl of halogen atom protection or by the hydroxyalkyl of protected silane；It is preferred that
Ground, R1For alkyl, hydroxyalkyl or by the hydroxyalkyl of protected silane.Silane in the hydroxyalkyl by protected silane is trimethyl
Silane, t-butyldimethyl silane, t-butyl diphenylsilane or dimethylphenylsilaneand.In formula of IV compound of the present invention
Branch with oxygen atom connection, can enhance the electron donation of donor, while to facilitate substance molten for the introducing of flexible branch
The raising of solution property.
Iii it) mix the compound of Formula IV that step ii) is obtained with the tetrahydrofuran steamed again after, is catalyzed in n-BuLi
Under, it is reacted with the n,N-Dimethylformamide steamed again, collection obtains compounds of formula V, and formula of V is as follows
Wherein R1For alkyl, hydroxyalkyl, by the hydroxyalkyl of halogen atom protection or by the hydroxyalkyl of protected silane；It is preferred that
Ground, R1For alkyl, hydroxyalkyl or by the hydroxyalkyl of protected silane.Silane in the hydroxyalkyl by protected silane is trimethyl
Silane, t-butyldimethyl silane, t-butyl diphenylsilane or dimethylphenylsilaneand.Formula of V compound tool of the present invention
There is good solubility property.
Iv compounds of formula V and 2,2- dicyano) are pitched into base -3- cyano -4- methyl -5-R2-5-R3Furans is anti-in ethanol
It answers, wherein R2For methyl or trifluoromethyl, R3For alkyl or phenyl, the organic second that collection obtains flexible isolating base group modification is non-
Linear optics chromophore.
Electron donor, conjugated pi electron bridge and electron acceptor of the invention can increase intermolecular steric hindrance after combining very well, press down
Because of the accumulation that dipole-dipole interaction generates between chromophore molecule processed, intramolecular electron transport ability is improved, is effectively improved
Conversion of the First-order Molecular Hyperpolarizability of chromophore molecule to material macroscopic view electro-optic coefficient.
According to the preferred embodiment of the present invention, the preparation method, specifically comprises the following steps:
1) under inert gas protection, by Compounds of formula II, R0- X and Anhydrous potassium carbonate are dissolved in anhydrous N, N- dimethyl
In formamide, temperature reaction is stirred, room temperature is down to after reaction, obtains solution A after deionized water is added；Solution A is extracted,
Merge organic phase, dry, filter, rotate, pillar layer separation, obtains compound of formula III after dry；
2) compound of formula III, thenyl triphenylphosphine and Cymag are dissolved in anhydrous ether, are stirred at room temperature
It mixes, product is poured into obtain solution B in ice water after completion of the reaction；Solution B is extracted, is dried, filtered, is rotated, column chromatography
Separation obtains compound of Formula IV after dry；
3) compound of Formula IV is dissolved in the tetrahydrofuran steamed again and obtains solution C, cooled down under inert gas protection, added
Enter n-BuLi, obtain solution D after stirring, the N steamed again is added into solution D, N- dimethylformamide obtains solution E, carries out
Stirring, is warmed to room temperature reaction again after stirring；It is terminated and is reacted with deionized water after completion of the reaction, obtain solution F；Solution F is carried out
Extraction, dries, filters, and rotates, pillar layer separation, obtains compounds of formula V after dry；
4) compounds of formula V and 2,2- dicyano are pitched into base -3- cyano -4- methyl -5-R2-5-R3Furans is dissolved in ethyl alcohol
Solution F is obtained, solution F is stirred at reflux reaction；Be cooled to room temperature, rotate, pillar layer separation after completion of the reaction, obtain it is flexible every
Organic second order non-linear optical chromophore from base group modification.
According to the preferred embodiment of the present invention, in step 1), the Compounds of formula II, R0- X and Anhydrous potassium carbonate
Molar ratio is 1~1.2:2:2.Invention technician has found in the course of the research, under the molar ratio, reaction be easier into
Row.Preferably, the Compounds of formula II, R0The molar ratio of-X and Anhydrous potassium carbonate is 1~1.2:2:2, in preferably ratio
Under range, obtained bearing reaction yield is higher.
According to the preferred embodiment of the present invention, in step 1), stirring is warming up to 100~150 DEG C, and the temperature is kept to stir
React 10~15h.Preferably, stirring is warming up to 110~135 DEG C, more preferably 110~120 DEG C.Preferably, mixing time is
11~13h, more preferably 11~12.5h.Under the conditions of more preferably mixing time and preferred temperature, the effect of reaction is more
It is good.
According to the preferred embodiment of the present invention, extracted described in step 1) extractant that uses be ethyl acetate, chloroform,
Methylene chloride or ether etc..Preferably, extractant is ethyl acetate in step 1), and invention technician sends out in the course of the research
Existing, the selection of extractant affects to separation purity.When extractant is ethyl acetate, the effect of extraction is optimal.
According to the preferred embodiment of the present invention, the dry desiccant used described in step 1) is anhydrous MgSO4Or
Na2SO4Deng.Preferably, desiccant is anhydrous MgSO in step 1)4.Invention technician has found in the course of the research, dry
The selection of agent has some impact on the acid-base property of solution.When desiccant is anhydrous MgSO4When, dry effect is optimal.
According to the preferred embodiment of the present invention, inert gas described in step 1) is nitrogen.
According to the preferred embodiment of the present invention, compound of formula III described in step 2), thenyl triphenylphosphine and
Molar ratio 1:1:15~30 of Cymag.Invention technician has found in the course of the research, select three's reactant and
Reaction ratio range is reacted, and yield is higher after reaction；Preferably, the compound of formula III, thenyl triphen
Base phosphine and Cymag are 1~1.3:1.5:18, and under preferably proportional region, obtained bearing reaction is high-efficient.
According to the preferred embodiment of the present invention, in step 2), mixing time be 8~for 24 hours.Preferably, mixing time 8
~18h, more preferably 10~15h.Under the conditions of more preferably mixing time, the effect not only reacted is more preferable, but also the production reacted
Rate is high.
According to the preferred embodiment of the present invention, it is ethyl acetate, dichloro that the extractant used is extracted described in step 2)
Methane or chloroform etc..Preferably, extractant is ethyl acetate in step 2), and invention technician has found in the course of the research,
The selection of extractant affects to the purity of product.When extractant is ether, the effect of extraction is optimal.
According to the preferred embodiment of the present invention, the dry desiccant used described in step 2) is anhydrous MgSO4Or
Na2SO4Deng.Preferably, desiccant is MgSO in step 2)4.Invention technician has found in the course of the research, desiccant
Selection affects to the acid-base property of solution.When desiccant is anhydrous MgSO4When, dry effect is optimal.
According to the preferred embodiment of the present invention, the solubility of solution C described in step 3) is 0.1~0.5mol/l, described
The concentration of solution D is 0.15~0.3mol/l, and the concentration of the solution E is 0.25~0.6mol/l.Invention technician exists
It is found in research process, the concentration of reactant will affect the yield of product；Preferably, the solubility of the solution C be 0.1~
0.15mol/l, the concentration of the solution D are 0.15~0.25mol/l, and the concentration of the solution E is 0.25~0.4mol/l,
Preferably under proportional region, obtained result is that the result of reaction is preferable, and yield is higher.
According to the preferred embodiment of the present invention, inert gas described in step 3) is nitrogen, and the cooling temperature is -70
~-80 DEG C.Invention technician has found in the course of the research, is cooled down using nitrogen to solution C, temperature can be made to drop to
It is sufficiently low, and safety and environmental protection.Preferably, the cooling temperature is -70~-80 DEG C, more preferably -72~-78 DEG C.More excellent
Cooling temperature under the conditions of, the effect not only reacted is more preferable, but also yield is higher.
According to the preferred embodiment of the present invention, mixing time is 1~2h after n-BuLi is added in step 3).It is preferred that
Ground, mixing time are 1~1.5h, more preferably 1.2~1.5h.Under the conditions of more preferably mixing time, not only mixed effect is more
It is good, and yield is higher.
It according to the preferred embodiment of the present invention, is 1~2h to solution E mixing time in step 3).Preferably, when stirring
Between be 1~1.5h, more preferably 1.2~1.5h.Under the conditions of more preferably mixing time, solution good mixing effect, yield is higher.
According to the preferred embodiment of the present invention, the reaction time in step 3) at room temperature is 20~40min.Preferably,
Reaction time is 20~35min, more preferably 25~30min.Under the conditions of the more preferably reaction time, the reaction knot that not only obtains
Fruit is more preferable, and the yield reacted is higher.
According to the preferred embodiment of the present invention, extracted described in step 3) extractant that uses be ethyl acetate, chloroform,
Methylene chloride and ether etc..Preferably, extractant is ethyl acetate in step 3), and invention technician sends out in the course of the research
Existing, the selection of extractant affects to the extraction purity of product.When extractant is ethyl acetate, the effect of extraction
It is optimal.
According to the preferred embodiment of the present invention, step 4) formula of V compound and 2,2- dicyano pitch base -3- cyano -
4- methyl -5-R2-5-R3The molar ratio of furans is 1~1.5:1.2~1.8, and invention technician has found in the course of the research,
Both the above reactant is selected to be reacted, reaction effect is good；Preferably, the compound D and 2,2- dicyano pitch base -3- cyanogen
Base -4- methyl -5-R2-5-R3The molar ratio of furans is 1~1.2:1.2~1.5, under preferably proportional region, obtained knot
Fruit reaction yield is high.
According to the preferred embodiment of the present invention, reaction temperature described in step 4) is 50~80 DEG C, the reaction time
For 4~6h.Preferably, reaction temperature is 55~75 DEG C, and the reaction time is 4~5.5h；More preferable reaction temperature is 60~70 DEG C,
Time is 4~5h.Under the conditions of more preferably reaction time and preferred temperature, the effect of reaction is more preferable.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions:
A kind of organic second order non-linear optical chromophore answering in optical signal modulation material of flexible isolating base group modification
With the optical signal modulation material passes through the organic second order non-linear optical chromophore and the doping preparation of unformed polycarbonate
It obtains.It is a discovery of the invention that the organic second order non-linear optical chromophore that the present invention is prepared is mixed with unformed polycarbonate
Miscellaneous obtained optical signal modulation material, the material thermal stability is high and can generate more stable electro-optic coefficient.
According to the preferred embodiment of the present invention, the organic second order non-linear optical chromophore and unformed polycarbonate
Mass ratio be 1:1~100.Preferably, the mass ratio is 1:3~10.Present invention discover that the mass ratio influences system
Stability, under preferred embodiment, obtained material is more excellent.
The present invention has in the preparation method of the organic second order non-linear optical chromophore of flexible isolating base group modification, reaction
The conditions such as the post-processing that the ratio of middle reactant, the mixing time of reaction, reaction terminate are both needed to strict control, only strict control
These good conditions could enable yield height, reaction effect that organic second order non-linear optical chromophore is prepared good.
It is that the primary technology overcome in the present invention is asked in addition, how to introduce the structure with oxygen atom branch into donor
Topic.In order to overcome the above technical problems, the present invention is by efficient reaction method, in modulation a large amount of by a series of accurate
Afterwards, flexible isolating group in being introduced into chromophore ensure that the unique structure of chromophore and preferable performance, finally
It is prepared for the material with preferable electro-optical properties.I.e. the technical scheme is that a unified entirety, each technical characteristic
It is not Line independent, can interacts between different technologies feature, therefore the realization of the final technical effect of the present invention, it is necessary to
Dependent on the entirety that can not be split of all technical characteristic organic integration, rather than the simple adduction of several technical characteristics.
In addition, unless otherwise specified, any range documented by the present invention includes any number between end value and end value
Any subrange that any number between value and end value or end value is constituted.
Beneficial effects of the present invention are as follows:
(1) knot of the organic second order non-linear optical chromophore and traditional chromophore with D- π-A structure of the invention
Structure is compared, and electron donor has selected introducing flexible isolating group on triphenylamine and its derivative, on the one hand has bigger sky
Between steric hindrance, can effectively reduce intermolecular interaction force, improve polarization efficiency, and then improve the single order of chromophore molecule
Molecular hyperpolarizability (β) is converted to the efficiency of macroscopical electro-optic coefficient, is furthermore possible to enhancing chromophore in conventional organic solvent
Dissolubility.
(2) electronics used in the organic second order non-linear optical chromophore provided by the invention with D- π-A structure is given
Body, conjugated pi electron bridge and electron acceptor combine rear intramolecular electron transport ability enhancing, and electro-optic coefficient can be improved
Transformation efficiency；In addition, the organic second order non-linear optical chromophore being prepared in the present invention and unformed polycarbonate adulterate
It can be used for synthetic polymer film, synthesized thin polymer film is as synthesis optical signal modulation materials'use, to meet device
Change and requires.
(3) synthesis step of the organic second order non-linear optical chromophore with D- π-A structure of the invention is simple, synthesis
Yield is high, with good dissolubility, higher thermal stability, with superelevation single order molecule super in most of organic solvents
Rate (β value) is converted to macroscopical electro-optic coefficient (r33) efficiency, with it is polymer-doped after intermolecular force is small, film forming
Well, the advantages that being easy to polarization and device, can be widely applied to electrooptical material field.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Embodiment 1
A kind of preparation of the organic second order non-linear optical chromophore CL of flexible isolating base group modification, the structure of CL are as follows:
Preparation route is as follows:
Specific step is as follows:
1) synthesis of compound 1, using Enhanced electro-optic activity from the
triarylaminophenyl-based chromophores by introducing heteroatoms to the donor
Method.
The phosphorus oxychloride of 1.0mL, that is, 11mmol is added dropwise in 5mL n,N-Dimethylformamide i.e. DMF at 0 DEG C, is stirred
After mixing reaction 2h, the DMF solution of the 10mL of the 3- methoxyl group triphenylamine dissolved with the i.e. 10.91mmol of 3.0g is slowly added dropwise thereto.
Reaction temperature is risen to 90 DEG C and is stirred to react 2h.After cooling, mixed solution is poured into cold water, and is added 1mol/l's
NaHCO3Solution adjusts pH until solution presentation neutrality, and is extracted with ethyl acetate, and merges organic phase, with anhydrous MgSO4It is dry
It is dry overnight, it then filters, filtered fluid is rotated and removes ethyl acetate, gained crude product is subjected to pillar layer separation, wherein petroleum
The volume ratio of ether and ethyl acetate is 80:1, obtains the compound solid compound 1 of yellow, yield 88%.
It is as follows to the Measurement results of compound 1:
1H NMR(500MHz,CDCl3) δ 3.69 (s, 3H), 6.45 (d, J=1.5,1H), 6.52-6.54 (dd, J=
8.5and 2,1H), 7.16-7.19 (m, 6H) 7.33-7.36 (t, 4H), 7.65-7.67 (dd, J=9 and 0.5,1H),
10.23(s,1H).
13C NMR(125MHz,CDCl3)55.39,101.74,112.22,118.21,125.15,126.44, 129.64,
129.88,146.13,154.84,163.09,187.79.
MS(EI):m/z calcd for C20H17NO2:303.4；found:303.1
2) synthesis of compound 2, method use Triphenylamine based new Schiff base ligand:
Solvent dependent selective fluorescence sensing of Mg2+and Fe3+ions。
In N2Protection in, the compound 1 of 1.0g, that is, 3.3mmol is dissolved in the anhydrous methylene chloride of 10ml, by reaction solution
- 78 DEG C are reduced to, the 1mL i.e. BBr of 9.9mmol is added dropwise3, after being added dropwise, 10h is stirred at this temperature, is heated up later
To room temperature, deionized water, quenching reaction is added.Mixed liquor is extracted with ethyl acetate, merges organic phase, with anhydrous MgSO4It is dry
It is dry overnight, it then filters, filtered fluid is rotated and removes ethyl acetate, gained crude product is subjected to pillar layer separation, wherein petroleum
The volume ratio of ether and ethyl acetate is 50:1, obtains the compound solid compound 2 of yellow, yield 92%.
It is as follows to the Measurement results of compound 2:
1H NMR(500MHz,CDCl3,d,ppm):11.40(s,1H,–CHO),9.58(s,1H, Ar–OH),7.34(m,
4H, Ar-H), 7.25 (d, J=8.5Hz, 1H, Ar-H), 7.25-7.18 (m, 6H, Ar-H), 6.45 (d, J=8.5Hz, 1H,
Ar-H), 6.34 (d, J=1.6Hz, 1H, Ar-H)
MS(EI):m/z calcd for C19H15NO2:289.3；found:289.1
3) synthesis of compound 3
In N2Protection in, the compound 2 of 2g, that is, 6.9mmol is dissolved in the anhydrous DMF of 25ml, into solution plus
Enter the 6- Mecoral and the 2g i.e. Anhydrous potassium carbonate of 13.6mmol of the i.e. 13.8mmol of 2g, stirring is warming up to 120 DEG C, at this temperature
12h is stirred, after completion of the reaction, room temperature is cooled to, injects deionized water, mixed liquor is extracted with ethyl acetate, merge organic phase,
With anhydrous MgSO4It is dried overnight, then filters, filtered fluid is rotated and removes ethyl acetate, gained crude product is subjected to column chromatography
Separation, wherein the volume ratio of petroleum ether and ethyl acetate is 50:1, obtains the compound solid compound 3 of yellow, yield is
86%.
It is as follows to the Measurement results of compound 3:
1H NMR (400MHz, Acetone) δ 10.26 (s, 1H), 7.59 (d, J=8.6Hz, 1H), 7.41 (t, J=
7.7Hz, 4H), 7.25 (m, 6H), 6.51 (s, 1H), 6.46 (d, J=8.7Hz, 1H), 3.88 (t, J=6.3Hz, 2H), 3.53
(t, J=6.0Hz, 2H), 3.38 (t, J=5.1Hz, 1H), 1.76 (m, 2H), 1.52 (m, 2H), 1.42 (m, 4H)
MS(EI):m/z calcd for C25H27NO3:389.5；found:389.2
4) synthesis of compound 4
Under nitrogen protection, by the bromination -2- thienyl-three of the compound 3 of 1.0g, that is, 2.6mmol and 1.24g, that is, 2.8mmol
Phenylphosphine is dissolved in 8ml and steams in tetrahydrofuran again, and the 0.81g i.e. NaH of 0.034 mol is then added, stirs at normal temperature for 24 hours,
It is poured slowly into the saturation NH of 100ml after completion of the reaction4Cl solution, is extracted with ether, by organic phase extracted with anhydrous MgSO4
It is dry, the organic phase after drying is filtered, revolving removes ether, by gained crude product pillar layer separation, wherein petroleum ether: second
The volume ratio of acetoacetic ester is 10:1, obtains yellow solid compound 4, yield 69% after dry.
It is as follows to the Measurement results of compound 4:
1H NMR (400MHz, Acetone) δ 7.31 (t, J=7.6Hz, 4H), 7.24 (d, J=6.5Hz, 2H), 7.11
(t, J=6.6Hz, 4H), 7.08 (t, J=4.9Hz, 2H), 7.06 (d, J=8.2Hz, 1H), 6.92 (t, J=3.9Hz, 1H),
6.73 (d, J=11.9Hz, 1H), 6.68 (s, 1H), 6.54 (d, J=8.3Hz, 1H), 6.49 (d, J=11.9Hz, 1H),
3.79 (t, J=6.3Hz, 2H), 3.49 (q, J=6.0Hz, 2H), 3.36 (t, J=5.0Hz, 1H), 1.62 (m, 2H), 1.58
(m,2H),1.40(m,4H).
MS(EI):m/z calcd for C30H31NO2S:469.6；found:469.2
5) synthesis of compound 5 shown in formula
The compound 4 of 0.50g, that is, 1.00mmol is dissolved in the THF that 10ml steams again, it is cooling with liquid nitrogen under nitrogen protection
To -78 DEG C, at the temperature and nitrogen protection, n-BuLi is slowly added dropwise into the THF solution steamed for being dissolved in compound 4 again
(2.2mL, 2.00mmol) after adding, stirs 1h at such a temperature, then adds dropwise the steaming again of the i.e. 3.60mmol of 0.26g
DMF, 1h is stirred to react at -78 DEG C, is then gradually heated to room temperature, reacts 1h；It is terminated after completion of the reaction with deionized water
Reaction, is extracted with ethyl acetate, by organic phase extracted with anhydrous MgSO4It is dried overnight, then filters, revolving removes acetic acid
Ethyl ester, by gained crude product pillar layer separation, wherein petroleum ether: the volume ratio of acetone is 5:1, obtains Red oil after dry
Liquid 5, yield 74%.
It is as follows to the Measurement results of red oil 5:
1H NMR (400MHz, Acetone) δ 9.87 (s, 1H), 7.84 (d, J=3.9Hz, 1H), 7.53 (d, J=
11.9Hz, 1H), 7.35 ((t, J=7.6Hz, 4H), 7.24 (d, J=3.9Hz, 1H), 7.21 (d, J=11.9Hz, 1H),
7.15 (m, 6H), 7.08 (d, J=8.8Hz, 1H), 6.79 (d, J=8.8Hz, 1H), 6.80 (s, 1H), 3.88 (t, J=
6.3Hz, 2H), 3.55 (q, J=6.0Hz, 2H), 3.38 (t, J=5.2Hz, 1H), 1.80 (m, 2H), 1.62 (m, 2H), 1.35
(m,4H).
MS(MALDI-TOF):m/z(M+,C31H31NO3S):calcd:497.6；found:497.2
6) synthesis of compound 6
In N2In protection, the compound 5 of 0.5g, that is, 1.0mmol is dissolved in the DMF solution of 10ml, is by 1.37g
The tert-butyl diphenyl chlorosilane of 5mmol and the 0.374 i.e. imidazoles of 5.5mmol are added in above-mentioned solution.By mixture in room temperature
For 24 hours, after completion of the reaction, a little deionized water is added, and be extracted with ethyl acetate in lower stirring, by organic phase extracted with anhydrous
MgSO4It being dried overnight, then filters, revolving removes ethyl acetate, by gained crude product pillar layer separation, wherein petroleum ether:
The volume ratio of acetone is 30:1, obtains dark yellow solid 6, yield 82% after dry.
It is as follows to the Measurement results of dark yellow solid 6:
1H NMR (400MHz, Acetone) δ 9.86 (s, 1H), 7.80 (d, J=3.9Hz, 1H), 7.70 (d, J=
6.9Hz, 4H), 7.53 (d, J=15.9Hz, 1H), 7.41 (t, J=7.2Hz, 4H), 7.32 (t, J=7.8 Hz, 4H), 7.26
(d, J=3.9Hz, 1H), 7.21 (d, J=16.0Hz, 1H), 7.15 (m, 6H), 7.06 (t, J=7.3Hz, 2H), 6.75 (d, J
=8.8Hz, 1H), 6.60 (d, J=8.8Hz, 1H), 6.56 (s, 1H), 3.85 (t, J=6.3Hz, 2H), 3.72 (t, J=
6.3Hz,2H),1.76(m,2H),1.62(m,2H),1.38 (m,4H),1.03(s,9H).
MS(MALDI-TOF):m/z(M+,C47H49NO3SSi):calcd:736.0；found:736.3
7) compound 7 is the synthesis of 3- hydroxy-3-methyl -2- butanone
The 98wt% concentrated sulfuric acid of 19ml is slowly mixed together with 100ml water, the mercury oxide of 13g yellow is then added, in 1.5h
It is interior, the 2- methyl -3- butyne-2-alcohol of 84g, that is, 1.0mol is added dropwise into 65-75 DEG C of the sulfuric acid solution containing mercury oxide, then exists
It is stirred to react 30min at 65-75 DEG C, is cooled to room temperature after completion of the reaction, reaction gains are filtered, filtered filtrate
It is extracted with 20mL ether, extraction is three times.Organic phase extracted is washed with water, sodium bicarbonate solution respectively, organic after washing
It is mutually dry with anhydrous magnesium sulfate, it then filters, filtered filtrate is distilled after concentrated by rotary evaporation, collects 140 DEG C of fractions, is done
The light yellow liquid that 45.6g is obtained after dry is compound 7, yield: 32.2%.
8) compound 8 is 2,2- dicyano methene base -3- cyano -4,5, the conjunction of 5- trimethyl furans electronics, that is, TCF receptor
At
The metallic sodium of 1.5g, that is, 0.065mol is dissolved in the dehydrated alcohol of 190ml, is added 6.7ml, that is, 0.064mol's
Then 20h is stirred at room temperature in the compound 6 and the 8.5g i.e. malononitrile of 0.13mol that step 7) obtains, revolving removes ethyl alcohol,
The water of 50ml is added after to revolving in resulting crude product, is then 4~5 with 6mol/l hydrochloric acid solution tune pH value, is precipitated a large amount of
Sepia grease；It after sufficiently being washed the grease with water, then twice with ethyl alcohol recrystallization, then dries, obtains 4.5g's
Pale yellow solid is compound 8, yield 35%.
9) synthesis of compound CL
It is anhydrous that the receptor TCF of the compound 6 of 0.28g, that is, 0.38mmol and 0.083g, that is, 0.42mmol is dissolved in 10ml
In ethyl alcohol, in 75 DEG C of reflux 6h, it is cooled to room temperature after completion of the reaction, revolving removes ethyl alcohol, by gained crude product pillar layer separation,
Wherein petrol ether/ethyl acetate=6:1 obtains blue solid powder compounds CL, yield 33% after dry.
The Measurement results of compound CL are as follows:
1H NMR(400MHz,CDCl3) δ 7.77 (d, J=15.6Hz, 2H), 7.65 (d, J=7.8,4H), 7.41 (d, J
=15.8Hz, 2H), 7.36 (d, J=7.3Hz, 4H), 7.34 (d, J=3.6Hz, 2H), 7.28 (m, 6H), 7.13 (d, J=
7.7Hz, 4H), 7.08 (t, J=7.3Hz, 2H), 6.99 (d, J=8.0Hz, 1H), 6.59 (d, J=8.0Hz, 1H), 6.57
(s, 1H), 3.82 (t, J=6.6Hz, 2H), 3.66 (t, J=6.4Hz, 2H), 1.76 (m, 2H), 1.72 (s, 6H), 1.60 (m,
6H),1.03(s,9H).
MS(MALDI-TOF):m/z(M+,C58H56N4O3SSi):calcd:917.2；found:917.4
What is obtained is had by the organic second order non-linear optical chromophore molecule with D- π-A structure of flexible branched modified
Good thermal stability；Have in the nonpolar solvents such as acetone, chloroform or ethyl alcohol isopolarity solvent and ether, six alkane of epoxy good
Good dissolubility.
Embodiment 2
A kind of preparation of thin polymer film, the method is as follows:
0.075 gram of unformed polycarbonate, that is, APC is added in 1.00mL methylene bromide, stirring 3~5h to APC is complete
After fully dissolved, organic second order non-linear optical chromophore compound CL synthesized by 0.025 gram of embodiment 1 is added, obtains organic
The mixed solution of second-order nonlinear optical chromophore compound and APC, by obtained mixed solution with rotation on ito glass substrate
Coating film, control revolving speed are 800~1200 turns/min, and then drying for 24 hours, is polymerize in 60 DEG C of vacuum oven
Object film I.The thickness of the polarized polymer thin film is between 2~4 μm.
Polarization and electro-optic coefficient measurement are carried out to synthesized thin polymer film
Corona polarizing is carried out to obtained thin polymer film I, poling temperature is 165 DEG C, and the polarization time is 10~20min,
Polarizing voltage is controlled in 10000~12000V or so；Electro-optic coefficient (r33) pass through decaying total reflection, i.e. document attenuated
Total reflection, ATR, referring to Yuan Bo, Cao Zhuangqi, Shen Qishun, et al., Real-time
measurement for electro-optic coefficient of a poled-polymer film in ATR
configuration,in Proceedings of SPIE-Optical Measurement and Nondestructive
Testing:Techniques and Applications,Nov 8-Nov 10 2000,Beijing,China,2000,134-
Method measurement in 138, the maximum electro-optic coefficient measured are 49pm/V.
Embodiment 3
A kind of preparation of the organic second order non-linear optical chromophore of flexible isolating base group modification, step is with embodiment 1, no
It is with place:
Without step 6, gained chromophore molecule is as follows:
Compared with Example 1, in the present embodiment in the organic second order non-linear optical chromophore of flexible isolating base group modification
Flexible isolating group be own hydroxyl, the end of the group is hydroxyl, though steric effect is not so good as the strong of big Silante terminated performance
It is strong, but be connected in main polymer chain or side chain for chromophore using condensation reaction and provide possibility.
Embodiment 4
A kind of preparation of thin polymer film, the method is as follows:
0.075 gram of unformed polycarbonate, that is, APC is added in 1.00mL methylene bromide, stirring 3~5h to APC is complete
After fully dissolved, organic second order non-linear optical chromophore compound CL-1 synthesized by 0.025 gram of embodiment 3 is added, is had
The mixed solution of machine second-order nonlinear optical chromophore compound and APC uses obtained mixed solution on ito glass substrate
Spin-coating method film, control revolving speed are 800~1200 turns/min, and then drying for 24 hours, is gathered in 60 DEG C of vacuum oven
Close object film I.The thickness of the polarized polymer thin film is between 2~4 μm.
Polarization and electro-optic coefficient measurement are carried out to synthesized thin polymer film
Corona polarizing is carried out to obtained thin polymer film I, poling temperature is 145 DEG C, and the polarization time is 10~20min,
Polarizing voltage is controlled in 10000~11000V or so；Electro-optic coefficient (r33) pass through decaying total reflection, i.e. document attenuated
Total reflection, ATR, referring to Yuan Bo, Cao Zhuangqi, Shen Qishun, et al., Real-time
measurement for electro-optic coefficient of a poled-polymer film in ATR
configuration,in Proceedings of SPIE-Optical Measurement and Nondestructive
Testing:Techniques and Applications,Nov 8-Nov 10 2000,Beijing,China,2000,134-
Method measurement in 138, the maximum electro-optic coefficient measured are 37pm/V.
Comparative example 1
A kind of organic second order non-linear optical chromophore, structure are
Flexible isolating group is not included in the chromophore, therefore the macroscopic view that the chromophore is shown in the material is arc
It can be only 16pm/V, well below macroscopical electro-optical activity of the chromophore in example 1 and example 3.
Conclusion: the organic second order non-linear optical chromophore in the present invention introduces flexible isolating group, and oxygen atom can
The electron performance of donor is improved, branch can be improved to cooperate between the advantages such as the dissolubility of chromophore, and synergistic effect makes
The impact of performance of its chromophore is optimal, and lacking to introduce, there is the flexible branch of oxygen atom to make chromophore in material in some aspects
The different degrees of decrease of the electrooptic effect presented in material.The electricity of product of the invention in the solubility property and material for improving material
Luminous effect etc. all has the effect of excellent.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of organic second order non-linear optical chromophore of flexible isolating base group modification, which is characterized in that have such as general formula I institute
The structure shown:
Wherein, R1For the alkyl of C1~C20, the hydroxyalkyl of C1~C10, the C1~C10 protected by halogen atom hydroxyalkyl or by
The hydroxyalkyl of C1~C10 of protected silane；
R2For methyl or trifluoromethyl；
R3For the alkyl or phenyl of C1~C20.
2. a kind of organic second order non-linear optical chromophore of flexible isolating base group modification according to claim 1, special
Sign is that the silane in the hydroxyalkyl by protected silane is trimethyl silane, t-butyldimethyl silane, tert-butyl hexichol
Base silane or dimethylphenylsilaneand.
3. a kind of organic second order non-linear optical chromophore of flexible isolating base group modification as described in claim 1~2 is any
Preparation method, which comprises the steps of:
I) in anhydrous n,N-Dimethylformamide, Compounds of formula II, R0- X and Carbon Dioxide nak response, collection obtain general formula
III compound；
Wherein, R0X is halogen atom, R in-X0For the alkyl of C1~C20 or the hydroxyalkyl of C1~C10；General formula II is as follows:
General formula III is as follows:
Wherein R1It is as defined above；
Ii compound of formula III, thenyl triphenylphosphine and the Cymag for) obtaining step i), react in anhydrous ether,
Collection obtains compound of Formula IV, and formula of IV is as follows
Wherein R1It is as defined above；
Iii) compound of Formula IV that step ii) is obtained is mixed with the tetrahydrofuran steamed again after, under n-BuLi catalysis, with
The n,N-Dimethylformamide reaction steamed again, collection obtain compounds of formula V, and formula of V is as follows
Wherein R1It is as defined above；
Iv compounds of formula V and 2,2- dicyano) are pitched into base -3- cyano -4- methyl -5-R2-5-R3Furans reacts in ethanol,
Wherein R2And R3As defined above, collection obtains the organic second order non-linear optical chromophore of flexible isolating base group modification.
4. a kind of preparation of the organic second order non-linear optical chromophore of flexible isolating base group modification according to claim 3
Method, which is characterized in that specifically comprise the following steps:
1) under inert gas protection, by Compounds of formula II, R0- X and Anhydrous potassium carbonate are dissolved in anhydrous N,N-dimethylformamide
In, stirring is warming up to 100~150 DEG C of 10~15h of reaction, and room temperature is down to after reaction, obtains solution A after deionized water is added；It is right
Solution A is extracted, and is merged organic phase, is dried, filtered, and is rotated, pillar layer separation, obtains compound of formula III after dry；
2) compound of formula III, thenyl triphenylphosphine and Cymag are dissolved in anhydrous ether, it is stirred at room temperature 8~
For 24 hours, product is poured into after completion of the reaction and obtains solution B in ice water；Solution B is extracted, is dried, filtered, is rotated, column chromatography
Separation obtains compound of Formula IV after dry；
3) compound of Formula IV is dissolved in the tetrahydrofuran steamed again and obtains solution C, be cooled to -70 under inert gas protection
~-80 DEG C, n-BuLi is added, obtains solution D after stirring 1~2h, the n,N-Dimethylformamide steamed again is added into solution D
Solution E is obtained, is warmed to room temperature 20~40min of reaction again after stirring 1~2h；It is terminated and is reacted with deionized water after completion of the reaction, obtained
To solution F；Solution F is extracted, is dried, filtered, is rotated, pillar layer separation, obtains compounds of formula V after dry；
4) compounds of formula V and 2,2- dicyano are pitched into base -3- cyano -4- methyl -5-R2-5-R3Furans, which is dissolved in ethyl alcohol, to be obtained
Solution F is stirred at reflux 4~6h of reaction at 50~80 DEG C；It is cooled to room temperature, rotates after completion of the reaction, pillar layer separation obtains soft
The organic second order non-linear optical chromophore of sexual isolation base group modification.
5. a kind of preparation of the organic second order non-linear optical chromophore of flexible isolating base group modification according to claim 4
Method, which is characterized in that in step 1), the inert gas is nitrogen, the Compounds of formula II, R0- X and Anhydrous potassium carbonate
Molar ratio be 1~2.5:2~5:2.5~5；It is described extract the extractant that uses be ethyl acetate, chloroform, methylene chloride or
Ether；The desiccant that the drying uses is anhydrous MgSO4Or Na2SO4。
6. a kind of preparation of the organic second order non-linear optical chromophore of flexible isolating base group modification according to claim 4
Method, molar ratio 1:1:15~30 of compound of formula III described in step 2), thenyl triphenylphosphine and Cymag；Institute
Stating the extractant that extraction uses is ethyl acetate, chloroform, methylene chloride or ether；The desiccant that the drying uses is anhydrous
MgSO4Or Na2SO4。
7. a kind of preparation of the organic second order non-linear optical chromophore of flexible isolating base group modification according to claim 4
Method, the solubility of solution C described in step 3) are 0.1~0.5mol/l, and the concentration of the solution D is 0.15~0.3mol/l,
The concentration of the solution E is 0.25~0.6mol/l；The inert gas is nitrogen；The extractant used that extracts is acetic acid
Ethyl ester, chloroform or methylene chloride.
8. a kind of preparation of the organic second order non-linear optical chromophore of flexible isolating base group modification according to claim 4
Method, step 4) formula of V compound and 2,2- dicyano pitch base -3- cyano -4- methyl -5-R2-5-R3The molar ratio of furans is
1~1.5:1.2~1.8.
9. a kind of organic second order non-linear optical chromophore of flexible isolating base group modification as described in claim 1 is in optical signal
Modulate the application in material, which is characterized in that the optical signal modulation material passes through the organic second-order non-linear optical color development
Group and the doping of unformed polycarbonate are prepared.
10. a kind of organic second order non-linear optical chromophore of flexible isolating base group modification according to claim 9 is answered
With, which is characterized in that the mass ratio of the organic second order non-linear optical chromophore and unformed polycarbonate is 1:1~100.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114656432A (en) * | 2022-04-01 | 2022-06-24 | 广州大学 | Self-assembled organic optical nonlinear chromophore and synthetic method and application thereof |
| CN115057852A (en) * | 2022-07-20 | 2022-09-16 | 河南大学 | Polarity-sensitive fluorescent probe, synthetic method and application of polarity-sensitive fluorescent probe as cancer cell migration diagnosis probe |
| CN115960093A (en) * | 2021-10-09 | 2023-04-14 | 香港城市大学深圳研究院 | Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device |
| US11634429B2 (en) | 2019-10-04 | 2023-04-25 | University Of Washington | Organic electro-optic chromophores |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845040A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Organic second-order non-linear optical chromophore with D-Pi-A structure and decorated by tree-like group, synthesizing method and application thereof |
| EP2021332B1 (en) * | 2006-05-03 | 2012-10-03 | Corning Incorporated | Mercaptofunctional high "mu-beta" eo chromophores and high tg, low optical loss, covalently bonded, polymers containing said chromophores and methods of synthesizing eo materials |
| CN102875546A (en) * | 2011-07-13 | 2013-01-16 | 中国科学院理化技术研究所 | Second-order nonlinear optical chromophore having D-pi-A structure and treating julolidine derivative as donor, and synthetic method and use thereof |
| CN104974151A (en) * | 2014-04-14 | 2015-10-14 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore containing azide group, synthetic method and application thereof |
| CN106279133A (en) * | 2015-06-11 | 2017-01-04 | 中国科学院理化技术研究所 | Organic second order non-linear optical chromophore and synthetic method and application |
-
2017
- 2017-07-24 CN CN201710606869.4A patent/CN109293643A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2021332B1 (en) * | 2006-05-03 | 2012-10-03 | Corning Incorporated | Mercaptofunctional high "mu-beta" eo chromophores and high tg, low optical loss, covalently bonded, polymers containing said chromophores and methods of synthesizing eo materials |
| CN101845040A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Organic second-order non-linear optical chromophore with D-Pi-A structure and decorated by tree-like group, synthesizing method and application thereof |
| CN102875546A (en) * | 2011-07-13 | 2013-01-16 | 中国科学院理化技术研究所 | Second-order nonlinear optical chromophore having D-pi-A structure and treating julolidine derivative as donor, and synthetic method and use thereof |
| CN104974151A (en) * | 2014-04-14 | 2015-10-14 | 中国科学院理化技术研究所 | Organic second-order nonlinear optical chromophore containing azide group, synthetic method and application thereof |
| CN106279133A (en) * | 2015-06-11 | 2017-01-04 | 中国科学院理化技术研究所 | Organic second order non-linear optical chromophore and synthetic method and application |
Non-Patent Citations (2)
| Title |
|---|
| CHEN, LU等: "Enhanced electro-optic activity from the triarylaminophenyl-based chromophores by introducing different steric hindrance groups", 《MATERIALS LETTERS》 * |
| 卡拉瑟斯等: "《当代有机合成方法》", 30 March 2006, 华东理工大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11634429B2 (en) | 2019-10-04 | 2023-04-25 | University Of Washington | Organic electro-optic chromophores |
| CN115960093A (en) * | 2021-10-09 | 2023-04-14 | 香港城市大学深圳研究院 | Optical chromophore compound, composite material containing optical chromophore compound, thin film and photoelectric integrated device |
| CN114656432A (en) * | 2022-04-01 | 2022-06-24 | 广州大学 | Self-assembled organic optical nonlinear chromophore and synthetic method and application thereof |
| CN114656432B (en) * | 2022-04-01 | 2023-05-26 | 广州大学 | Self-assembled organic optical nonlinear chromophore, and synthesis method and application thereof |
| CN115057852A (en) * | 2022-07-20 | 2022-09-16 | 河南大学 | Polarity-sensitive fluorescent probe, synthetic method and application of polarity-sensitive fluorescent probe as cancer cell migration diagnosis probe |
| CN115057852B (en) * | 2022-07-20 | 2023-09-05 | 河南大学 | Polarity-sensitive fluorescent probe, synthesis method and application of polarity-sensitive fluorescent probe as cancer cell migration diagnostic probe |
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