CN103664933B - organic electro-optic chromophore containing electron donor and synthetic method thereof - Google Patents
organic electro-optic chromophore containing electron donor and synthetic method thereof Download PDFInfo
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- CN103664933B CN103664933B CN201210323766.4A CN201210323766A CN103664933B CN 103664933 B CN103664933 B CN 103664933B CN 201210323766 A CN201210323766 A CN 201210323766A CN 103664933 B CN103664933 B CN 103664933B
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 24
- 239000000243 solution Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 14
- 229940043279 diisopropylamine Drugs 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- -1 aniline compound Chemical class 0.000 claims description 7
- OGOXSGSVUVOJNZ-UHFFFAOYSA-N C1(CCCCC1)N1C(C1=O)=O Chemical compound C1(CCCCC1)N1C(C1=O)=O OGOXSGSVUVOJNZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 150000003053 piperidines Chemical group 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000382 optic material Substances 0.000 abstract 2
- 239000012792 core layer Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000004440 column chromatography Methods 0.000 description 18
- 239000000741 silica gel Substances 0.000 description 18
- 229910002027 silica gel Inorganic materials 0.000 description 18
- 239000002594 sorbent Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 229960000935 dehydrated alcohol Drugs 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000011368 organic material Substances 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 230000009881 electrostatic interaction Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 0 BC(C(C=CC=C(CC(C)(C)C1)C(*)=C1C=Cc1cc(C(C)(C)CC2)c3N2CCC(C)(C)c3c1*)=C1*)(OC1=C(C#N)C#N)I Chemical compound BC(C(C=CC=C(CC(C)(C)C1)C(*)=C1C=Cc1cc(C(C)(C)CC2)c3N2CCC(C)(C)c3c1*)=C1*)(OC1=C(C#N)C#N)I 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- QHQSVMOJQYNXSO-UHFFFAOYSA-N 2-butyl-3,5,5-trimethylcyclohex-2-en-1-one Chemical compound CCCCC1=C(C)CC(C)(C)CC1=O QHQSVMOJQYNXSO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- PSVBHJWAIYBPRO-UHFFFAOYSA-N lithium;niobium(5+);oxygen(2-) Chemical compound [Li+].[O-2].[O-2].[O-2].[Nb+5] PSVBHJWAIYBPRO-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D455/00—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
- C07D455/03—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
- C07D455/04—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine
-
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract
The invention relates to the field of organic electro-optic materials, in particular to a high-performance organic electro-optic chromophore containing an electron donor and a synthetic method thereof. The high-performance organic electro-optic chromophore containing the electron donor can be doped or hung in a proper polymer system to form an electro-optic material, and can be used as a core layer for manufacturing an electro-optic device. The high-performance organic electro-optic chromophore containing the electron donor has the following structural formula.
Description
Technical field
The present invention relates to electro-optical organic material field, particularly a class contains high performance Organic electro-optic chromophore and the synthetic method thereof of electron donor(ED).
Background technology
In fields such as optical communication and optical signal processes, electro-optic conversion is indispensable technique means.And electrooptical material is as the key components of electro-optical device, conclusive effect is played to electro-optic conversion.At present, practical electrooptical material mainly inorganic Lithium niobium trioxide material.Organic materials has compared with inorganic materials that nonlinear optical coefficients are large, fast response time, optical damage threshold are high, can carry out molecular designing as requested, be easy to the advantages such as processing and cheapness.The device adopting electro-optical organic material to make has low half-wave voltage (lower than 1V) and ultra high bandwidth (expection bandwidth is 350GHz), is more suitable for the growth requirement of field of information communication high speed, heavy body.
In electro-optical organic material system, the Electro optic chromophore as functional group affects the electro-optical properties of material, stability and absorption loss etc., and then impacts the device of preparation.And electro-optic coefficient is the main performance index of electrooptical material.By molecular designing, make chromophoric group have high nonlinear optics single order molecular hyperpolarizability (β value) and modify Electro optic chromophore molecule, reduce macroscopical electro-optic coefficient that intermolecular electrostatic interaction all can improve material.
The patent about electro-optical organic material reported has many, as US6067186.But wherein the electro-optic coefficient of most of electro-optical organic material is not very high.The present invention have employed new electron donor(ED) in molecular designing, and it has strong electron donation and large sterically hindered.Like this, chromophoric β value not only improves greatly, and reduces intermolecular electrostatic interaction due to sterically hindered, has also increased considerably macroscopical electro-optic coefficient of material.Adopt Organic electro-optic chromophore prepared by the present invention, be doped in polymkeric substance, the electro-optic coefficient recorded reaches 120-240pm/V.
Summary of the invention
A class is the object of the present invention is to provide to contain the high performance Organic electro-optic chromophore of electron donor(ED).
Another object of the present invention is to provide a kind of synthetic method of the high performance Organic electro-optic chromophore containing electron donor(ED).
High performance Organic electro-optic chromophore containing electron donor(ED) of the present invention has following structure:
Wherein:
Alkyl, benzyl, the-(CH of X to be carbonatoms be 1-10
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl;
A is H, OR
1or SR
1, wherein: R
1for carbonatoms is the alkyl of 1-10;
B
1for CH
3or CF
3; B
2for CH
3, phenyl or 2-(5-phenyl) thienyl.
The synthetic method of the high performance Organic electro-optic chromophore containing electron donor(ED) of the present invention comprises the following steps:
1) by the amino benzenes compounds shown in structural formula 1, halides, (Y-X, Y are Cl or Br; X is benzyl, carbonatoms is 1-10 alkyl ,-(CH
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl), hexaoxacyclooctadecane-6-6 and Anhydrous potassium carbonate react (time of General reactions is 1-10 hour) in DMF (DMF) under 40-100 DEG C of nitrogen atmosphere; Wherein, amino benzenes compounds: halides: hexaoxacyclooctadecane-6-6: the mol ratio of Anhydrous potassium carbonate is 1:1:0.2:1.5; Add in products therefrom water (water yield indefinite, add water be in order to after diluting for extraction), with steaming vibrating dichloromethane after dichloromethane extraction, dry (available anhydrous MgSO
4), pillar layer separation, obtains the compound shown in structural formula 2;
Wherein: X is benzyl, carbonatoms is 1-10 alkyl ,-(CH
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl;
2) by step 1) compound shown in structural formula 2, the isophorone shown in structural formula 3 and the sodium hydroxide (or sodium alkoxide) that obtain in the mixing solutions (water: the volume ratio of ethanol is 1:4) of water and ethanol in stirring at room temperature (the general time of stirring is 140-145 hour), wherein, the compound shown in structural formula 2: the isophorone shown in structural formula 3: the mol ratio of sodium hydroxide (or sodium alkoxide) is 1:1:2; Boil off water and ethanol; The ethyl acetate of resistates heat (general temperature is preferably about 50 DEG C) extracts rear concentrated evaporate to dryness, and pillar layer separation, obtains the compound shown in structural formula 4;
Wherein: X is benzyl, carbonatoms is 1-10 alkyl ,-(CH
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl;
A is H, OR
1or SR
1in one, R
1for carbonatoms is the alkyl of 1-10;
3) diisopropylamine to be dissolved in anhydrous diethyl ether (preferred diisopropylamine be dissolved in be its about 3 times volumes anhydrous diethyl ether in), and be chilled to 0 DEG C, drip wherein and obtain lithium diisopropyl amido solution (LDA) with the equimolar n-butyllithium solution of diisopropylamine (organic solvent dissolving n-Butyl Lithium can be normal hexane); Above-mentioned lithium diisopropyl amido solution is chilled to-50 DEG C; To instill wherein with lithium diisopropyl amido equimolar N-cyclohexyl acetimide, the mixed solution obtained is chilled to after being warming up to 0 DEG C-78 DEG C (preferably coolings at once) again; Be dissolved in the compound shown in the equimolar structural formula 4 of diisopropylamine in anhydrous tetrahydro furan (THF), be then added drop-wise in the mixed solution of above-mentioned-78 DEG C, after dropwising by temperature to room temperature, and stir and spend the night and obtain reaction solution; The aqueous acetic acid of 1N is dripped in above-mentioned reaction solution, then by reactant impouring water, petroleum ether extraction; Dry (available anhydrous Na
2sO
4carry out drying) gained solution, pillar layer separation, obtains the compound shown in structural formula 5;
Wherein: X is benzyl, carbonatoms is 1-10 alkyl ,-(CH
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl;
A is H, OR
1or SR
1in one, R
1for carbonatoms is the alkyl of 1-10;
4) by step 3) compound (donor compound 5) shown in structural formula 5 that obtains and with compound (acceptor compound) back flow reaction (time of general back flow reaction is 1-10 hour) in organic solvent (organic solvent can be selected from the one in ethanol, methyl alcohol, tetrahydrofuran (THF) and trichloromethane) shown in the structural formula 6 of its equimolar ratio; Boil off organic solvent after completion of the reaction, pillar layer separation can obtain final product (the high performance Organic electro-optic chromophore containing electron donor(ED) shown in structural formula 7);
Wherein:
Alkyl, benzyl, the-(CH of X to be carbonatoms be 1-10
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl;
A is H, OR
1or SR
1in one, wherein: R
1for carbonatoms is the alkyl of 1-10;
B
1for CH
3or CF
3; B
2for CH
3, phenyl or 2-(5-phenyl) thienyl.
Step 4) described in the compound shown in structural formula 5 and with the compound back flow reaction in organic solvent shown in the structural formula 6 of its equimolar ratio, be in catalyst-free or the back flow reaction of carrying out under having the catalyzer of catalytic amount to exist; Described catalyzer can be piperidines or triethylamine etc.
In synthetic method of the present invention, used various reaction raw materials are commercially available prod.High performance Organic electro-optic chromophore containing electron donor(ED) of the present invention can adulterate or be articulated in suitable polymkeric substance (as APC, PMMA) system and form electrooptical material, and is used for the making of electro-optical device as sandwich layer.
The invention has the advantages that:
1) electron donor(ED) of the high performance Organic electro-optic chromophore containing electron donor(ED) of the present invention has strong electron donation, can improve the nonlinear optics single order molecular hyperpolarizability of organic chromophores.In addition, the electron donor(ED) of organic chromophores molecule has large sterically hindered, reduces intermolecular electrostatic interaction, thus can improve macroscopical electro-optic coefficient of material.
2) acceptor of the high performance Organic electro-optic chromophore containing electron donor(ED) of the present invention have employed strong electron-withdrawing group, can increase substantially the electro-optic coefficient of material.
Embodiment
Embodiment 1
Synthesize the Organic electro-optic chromophore 1 of following structure:
Synthetic route is as follows:
Synthetic method is:
1). the synthesis of the compound 2 shown in structural formula 2
By the compound 1 shown in 3.9g structural formula 1,1.9g n-bromide butane, 0.76g hexaoxacyclooctadecane-6-6 and the anhydrous k of 3g
2cO
3react 2 hours under 60 DEG C of nitrogen atmosphere in 80mlDMF solution; After completion of the reaction, in products therefrom, add water, with steaming vibrating dichloromethane after dichloromethane extraction, anhydrous MgSO
4dry.The compound 2 shown in 4.5g structural formula 2 is obtained after column chromatography (sorbent material is silica gel) is separated;
2). the synthesis of the compound 3 shown in structural formula 3
By 4.5g step 1) compound 2 shown in structural formula 2,1.1g sodium hydroxide and the 1.9g isophorone that obtain in the mixing solutions of 5ml water and 20ml ethanol in stirring at room temperature about 6 days; Revolve and steam except anhydrating and ethanol; Resistates temperature is concentrated evaporate to dryness after the ethyl acetate of about 50 DEG C is extracted, and column chromatography (sorbent material is silica gel) is separated, and obtains the compound 3 shown in 2.5g structural formula 3;
3). the synthesis of the compound 4 shown in structural formula 4
1.2ml diisopropylamine is dissolved in the dry anhydrous diethyl ether of 3.6ml, and is chilled to 0 DEG C; Drip the 2.4M n-butyllithium solution (being dissolved in normal hexane) of 3.6ml wherein, obtain lithium diisopropyl amido solution (LDA), above-mentioned LDA solution is chilled to-50 DEG C; By the instillation of the N-cyclohexyl acetimide of 1.3ml wherein, the mixed solution obtained is chilled to-78 DEG C after being warming up to 0 DEG C again; By according to step 2) the compound 3 shown in 3.8g structural formula 3 prepared of method be dissolved in anhydrous THF, be then added drop-wise in the mixed solution of above-mentioned-78 DEG C; After dropwising, by the temperature of solution to room temperature, and stir and spend the night and obtain reaction solution; The aqueous acetic acid of 1N is dripped in above-mentioned reaction solution, then by reactant impouring water, petroleum ether extraction; Gained solution anhydrous Na
2sO
4after dry, column chromatography (sorbent material is silica gel) is separated; Obtain the compound 4 shown in 2.1g structural formula 4;
4). the synthesis of Organic electro-optic chromophore 1
By 0.2g step 3) compound 4 shown in structural formula 4,0.08g TCF and the 5mg piperidines that obtain back flow reaction 10 hours in 2ml trichloromethane; Boil off trichloromethane, column chromatography (sorbent material is silica gel) is separated, and obtains the Organic electro-optic chromophore 1 product 0.18g shown in structure above.λ
max(CHCl
3):756nm；M
+:656；
1HNMR(CDCl
3):δ8.01(t,1H),7.39(s,1H),7.06(d,1H),6.84(d,1H),6.38(d,1H),6.34(d,1H),6.30(s,1H),3.81(t,2H),3.19(m,4H),2.43(d,4H),1.86(m,2H),1.73(t,4H),1.70(s,6H),1.56(m,2H),1.42(s,6H),1.30(s,6H),1.06(s,6H),1.02(t,3H)。
Embodiment 2
Synthesize the Organic electro-optic chromophore 2 of following structure:
Synthetic route is as follows:
Synthetic method is:
Basic with embodiment 1, just by 0.1g embodiment 1 step 3) compound 4 shown in structural formula 4 that obtains and 0.08g SF-TCF back flow reaction 0.5 hour in 1ml dehydrated alcohol; Boil off dehydrated alcohol, column chromatography (sorbent material is silica gel) is separated, and obtains the Organic electro-optic chromophore 2 product 0.1g shown in structure above.λ
max(CHCl
3):995nm；M
+:854；
1HNMR(CDCl
3):δ8.25(br,1H),7.59(d,2H),7.41(d,2H),7.39(s,1H),7.36(m,3H),6.91(d,1H),6.83(d,1H),6.73(s,1H),6.44(d,1H),6.34(d,1H),3.81(t,2H),3.26(m,4H),2.45(s,2H),2.40(m,2H),1.86(m,2H),1.73(t,4H),1.56(m,2H),1.42(s,6H),1.30(s,6H),1.03(t,3H),0.99(s,6H)。
Embodiment 3
Synthesize the Organic electro-optic chromophore 3 of following structure:
Synthetic route is as follows:
Synthetic method is:
Basic with embodiment 1, just by 0.1g embodiment 1 step 3) compound 4 shown in structural formula 4 that obtains and 0.066g PF-TCF back flow reaction 0.5 hour in 1ml dehydrated alcohol; Boil off dehydrated alcohol, column chromatography (sorbent material is silica gel) is separated, and obtains the Organic electro-optic chromophore 3 product 0.11g shown in structure above.λ
max(CHCl
3):973nm；M
+:772；
1HNMR(CDCl
3):δ8.02(br,1H),7.49(m,5H),7.41(s,1H),7.26(d,1H),7.22(d,1H),6.38(d,1H),6.31(s,1H),6.26(d,1H),3.81(t,2H),3.26(m,4H),2.45(s,2H),2.30(q,2H),1.86(m,2H),1.72(t,4H),1.56(m,2H),1.42(s,6H),1.30(s,6H),1.02(t,3H),0.97(s,6H)。
Embodiment 4
Synthesize the Organic electro-optic chromophore 4 of following structure:
Synthetic route is as follows:
Synthetic method is:
1). the synthesis of the compound 5 shown in structural formula 5
By 2.0g embodiment 1 step 1) compound 2 shown in structural formula 2,0.66g sodium ethylate and the 1g methoxyl group isophorone that obtain in the mixing solutions of 2ml water and 8ml ethanol in stirring at room temperature about 6 days; Revolve and steam except anhydrating and ethanol; Resistates temperature is concentrated evaporate to dryness after the ethyl acetate of about 50 DEG C is extracted, and column chromatography (sorbent material is silica gel) is separated, and obtains the compound 5 shown in 1.2g structural formula 5;
2). the synthesis of the compound 6 shown in structural formula 6
1.2ml diisopropylamine is dissolved in the dry anhydrous diethyl ether of 3.6ml, and is chilled to 0 DEG C; Drip the 2.4M n-butyllithium solution (being dissolved in normal hexane) of 3.6ml wherein, obtain lithium diisopropyl amido solution (LDA), above-mentioned LDA solution is chilled to-50 DEG C; By the instillation of the N-cyclohexyl acetimide of 1.3ml wherein, the mixed solution obtained is chilled to-78 DEG C after being warming up to 0 DEG C again; By according to step 1) the compound 5 shown in 4.1g structural formula 5 prepared of method be dissolved in anhydrous THF, be then added drop-wise in the mixed solution of above-mentioned-78 DEG C; After dropwising, by the temperature of solution to room temperature, and stir and spend the night and obtain reaction solution; The aqueous acetic acid of 1N is dripped in above-mentioned reaction solution, then by reactant impouring water, petroleum ether extraction; Gained solution anhydrous Na
2sO
4after dry, column chromatography (sorbent material is silica gel) is separated; Obtain the compound 6 shown in 2.1g structural formula 6;
3). the synthesis of Organic electro-optic chromophore 4
By 0.1g step 2) compound 6 shown in structural formula 6 that obtains and 0.08g SF-TCF back flow reaction 0.5 hour in 1ml dehydrated alcohol; Boil off dehydrated alcohol, column chromatography (sorbent material is silica gel) is separated, and obtains the Organic electro-optic chromophore 4 product 0.09g shown in structure above.λ
max(CHCl
3):999nm；M
+:884；
1HNMR(CDCl
3):δ8.24(br,1H),7.59(d,2H),7.41(d,2H),7.39(s,1H),7.36(m,3H),7.28(d,1H),6.83(d,1H),6.79(d,1H),6.44(d,1H),3.82(t,2H),3.71(s,3H),3.27(m,4H),2.49(s,2H),2.45(m,2H),1.86(m,2H),1.73(t,4H),1.56(m,2H),1.42(s,6H),1.30(s,6H),1.03(t,3H),0.99(s,6H)。
Embodiment 5
Synthesize the Organic electro-optic chromophore 5 of following structure:
Synthetic route is as follows:
Synthetic method is:
1). the synthesis of the compound 7 shown in structural formula 7
By 2.0g embodiment 1 step 1) compound 2 shown in structural formula 2,0.66g sodium ethylate and the 1.4g 2-S butyl-isophorone that obtain in the mixing solutions of 2ml water and 8ml ethanol in stirring at room temperature about 6 days; Revolve and steam except anhydrating and ethanol; Resistates is concentrated evaporate to dryness after extracting with hot ethyl acetate, and column chromatography (sorbent material is silica gel) is separated, and obtains the compound 7 shown in 1.1g structural formula 7;
2). the synthesis of the compound 8 shown in structural formula 8
1.2ml diisopropylamine is dissolved in the dry anhydrous diethyl ether of 3.6ml, and is chilled to 0 DEG C; Drip the 2.4M n-butyllithium solution (being dissolved in normal hexane) of 3.6ml wherein, obtain lithium diisopropyl amido solution (LDA), above-mentioned LDA solution is chilled to-50 DEG C; By the instillation of the N-cyclohexyl acetimide of 1.3ml wherein, the mixed solution obtained is chilled to-78 DEG C after being warming up to 0 DEG C again; By according to step 1) the compound 7 shown in 4.6g structural formula 7 prepared of method be dissolved in anhydrous THF, be then added drop-wise in the mixed solution of above-mentioned-78 DEG C; After dropwising, by the temperature of solution to room temperature, and stir and spend the night and obtain reaction solution; The aqueous acetic acid of 1N is dripped in above-mentioned reaction solution, then by reactant impouring water, petroleum ether extraction; Gained solution anhydrous Na
2sO
4after dry, column chromatography (sorbent material is silica gel) is separated; Obtain the compound 8 shown in 2.4g structural formula 8;
3). the synthesis of Organic electro-optic chromophore 5
By 0.1g step 2) compound 8 shown in structural formula 8 that obtains and 0.07g SF-TCF back flow reaction 0.5 hour in 1ml dehydrated alcohol; Boil off dehydrated alcohol, column chromatography (sorbent material is silica gel) is separated, and obtains the Organic electro-optic chromophore 5 product 0.08g shown in structure above.λ
max(CHCl
3):978nm；M
+:942。
Embodiment 6
Synthesize the Organic electro-optic chromophore 6 of following structure:
Synthetic route is as follows:
Synthetic method is:
1). the synthesis of the compound 9 shown in structural formula 9
By the compound 1 shown in 4.0g structural formula 1,3.7g Cl (CH
2)
6oSi (CH
3)
2(t-C
4h
9), 0.8g hexaoxacyclooctadecane-6-6 and the anhydrous k of 3g
2cO
3react 3 hours under 60 DEG C of nitrogen atmosphere in 80mlDMF solution; After completion of the reaction, in products therefrom, add water, with steaming vibrating dichloromethane after dichloromethane extraction, anhydrous MgSO
4dry.The compound 9 shown in 6.9g structural formula 9 is obtained after column chromatography (sorbent material is silica gel) is separated; Above-mentioned t-C
4h
9for the tertiary butyl
2). the synthesis of the compound 10 shown in structural formula 10
By 6.9g step 1) compound 9 shown in structural formula 9,1.1g sodium hydroxide and the 1.9g isophorone that obtain in the mixing solutions of 8ml water and 32ml ethanol in stirring at room temperature about 6 days; Revolve and steam except anhydrating and ethanol; Resistates temperature is concentrated evaporate to dryness after the ethyl acetate of about 50 DEG C is extracted, and column chromatography (sorbent material is silica gel) is separated, and obtains the compound 10 shown in 3.3g structural formula 10;
3). the synthesis of the compound 11 shown in structural formula 11
1.2ml diisopropylamine is dissolved in the dry anhydrous diethyl ether of 3.6ml, and is chilled to 0 DEG C; Drip the 2.4M n-butyllithium solution (being dissolved in normal hexane) of 3.6ml wherein, obtain lithium diisopropyl amido solution (LDA), above-mentioned LDA solution is chilled to-50 DEG C; By the instillation of the N-cyclohexyl acetimide of 1.3ml wherein, the mixed solution obtained is chilled to-78 DEG C after being warming up to 0 DEG C again; By according to step 2) the compound 10 shown in 5.2g structural formula 10 prepared of method be dissolved in anhydrous THF, be then added drop-wise in the mixed solution of above-mentioned-78 DEG C; After dropwising, by the temperature of solution to room temperature, and stir and spend the night and obtain reaction solution; The aqueous acetic acid of 1N is dripped in above-mentioned reaction solution, then by reactant impouring water, petroleum ether extraction; Gained solution anhydrous Na
2sO
4after dry, column chromatography (sorbent material is silica gel) is separated; Obtain the compound 11 shown in 2.6g structural formula 11;
4). the synthesis of Organic electro-optic chromophore 6
By 0.1g step 3) compound 11 shown in structural formula 11 that obtains and 0.05g PF-TCF back flow reaction 0.5 hour in 1ml dehydrated alcohol; Boil off dehydrated alcohol, column chromatography (sorbent material is silica gel) is separated, and obtains the Organic electro-optic chromophore 6 product 0.08g shown in structure above.λ
max(CHCl
3):970nm；M
+:930。
Embodiment 7
Synthesize the Organic electro-optic chromophore 7 of following structure:
Synthetic route is as follows:
Synthetic method is:
1). the synthesis of the compound 12 shown in structural formula 12
Compound 11 shown in the structural formula 11 that 0.1g embodiment 6 is obtained, in the 10ml methyl alcohol containing 2ml 2N hydrochloric acid stir 2 hours, in and hydrochloric acid after, boil off methyl alcohol, column chromatography (sorbent material is silica gel) is separated, and obtains the compound 12 shown in 0.06g structural formula 12.
2). the synthesis of Organic electro-optic chromophore 7
By 0.06g step 1) compound 12 shown in structural formula 12 that obtains and 0.04g PF-TCF back flow reaction 0.5 hour in 1ml dehydrated alcohol; Boil off dehydrated alcohol, column chromatography (sorbent material is silica gel) is separated, and obtains the Organic electro-optic chromophore 7 product 0.05g shown in structure above.λ
max(CHCl
3):976nm；M
+:816。
Embodiment 8
1). the preparation of electro-optic polymer film
The 20mg Organic electro-optic chromophore 1 embodiment 1 obtained and 0.1g polycarbonate (APC) are dissolved in 1ml vinyl trichloride, adopt spin-coating method, ito glass are coated with thickness is about the film of 4 μm.Film, in 50 DEG C of vacuum-dryings 24 hours, obtains electro-optic polymer film.
2). the polarization of electro-optic polymer film
First in step 1) polymeric film surface that obtains sputters the gold that a layer thickness is about 200nm, then adopts contact polarization method to polarize to electro-optic polymer film.By electro-optic polymer film heating to second-order transition temperature (120 DEG C), between gold electrode and ITO electrode, apply the voltage of 400V, keep 5 minutes, then under the voltage of 400V, make temperature be down to room temperature, close voltage.
3). electro-optic coefficient measures
The simple reflex method electro-optic polymer film good to above-mentioned polarization is adopted to carry out the mensuration of electro-optic coefficient.Light source is the laser of 1310nm, electro-optic coefficient r
33calculated by following formula:
Wherein, λ is optical wavelength, and θ is input angle, I
cfor output light intensity modulation amplitude, I
mfor modulation amplitude, V
mfor modulating voltage, n is specific refractory power.The electro-optic coefficient recording above-mentioned polarized polymer thin film is 110pm/V.
Claims (10)
1. the Organic electro-optic chromophore containing electron donor(ED), is characterized in that, the described Organic electro-optic chromophore containing electron donor(ED) has following structure:
Wherein:
Alkyl, benzyl, the-(CH of X to be carbonatoms be 1-10
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl;
A is H, OR
1or SR
1, wherein: R
1for carbonatoms is the alkyl of 1-10;
B
1for CH
3or CF
3; B
2for CH
3, phenyl or 2-(5-phenyl) thienyl.
2. a synthetic method for the Organic electro-optic chromophore containing electron donor(ED) according to claim 1, it is characterized in that, described synthetic method comprises the following steps:
1) aniline compound, halides, hexaoxacyclooctadecane-6-6 and the Anhydrous potassium carbonate shown in structural formula 1 is reacted in DMF under 40-100 DEG C of nitrogen atmosphere; Wherein, aniline compound: halides: hexaoxacyclooctadecane-6-6: the mol ratio of Anhydrous potassium carbonate is 1:1:0.2:1.5; In products therefrom, add water, with steaming vibrating dichloromethane after dichloromethane extraction, dry, pillar layer separation, obtains the compound shown in structural formula 2;
Wherein:
Halides Y-X represents, Y is Cl or Br; X is benzyl, carbonatoms is 1-10 alkyl ,-(CH
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, n=1-10, t-C
4h
9for the tertiary butyl;
2) by step 1) compound shown in structural formula 2, the isophorone shown in structural formula 3 and the sodium hydroxide that obtain or sodium alkoxide in the mixing solutions of water and ethanol in stirring at room temperature, wherein, the compound shown in structural formula 2: the isophorone shown in structural formula 3: the mol ratio of sodium hydroxide or sodium alkoxide is 1:1:2; Boil off water and ethanol; The ethyl acetate of resistates heat extracts rear concentrated evaporate to dryness, and pillar layer separation, obtains the compound shown in structural formula 4;
3) diisopropylamine is dissolved in anhydrous diethyl ether, and is chilled to 0 DEG C, drip wherein and obtain lithium diisopropyl amido solution with the equimolar n-butyllithium solution of diisopropylamine; Above-mentioned lithium diisopropyl amido solution is chilled to-50 DEG C; To instill wherein with lithium diisopropyl amido equimolar N-cyclohexyl acetimide, the mixed solution obtained is chilled to-78 DEG C after being warming up to 0 DEG C again; By being dissolved in anhydrous tetrahydro furan with the compound shown in the equimolar structural formula 4 of diisopropylamine, be then added drop-wise in the mixed solution of above-mentioned-78 DEG C, after dropwising by temperature to room temperature, and stir and spend the night and obtain reaction solution; The aqueous acetic acid of 1N is dripped in above-mentioned reaction solution, then by reactant impouring water, petroleum ether extraction; Dry gained solution, pillar layer separation, obtains the compound shown in structural formula 5;
4) by step 3) compound shown in structural formula 5 that obtains and with the compound back flow reaction in organic solvent shown in the structural formula 6 of its equimolar ratio; Boil off organic solvent after completion of the reaction, pillar layer separation, obtain the Organic electro-optic chromophore containing electron donor(ED) shown in structural formula 7;
Wherein, in structure above:
Alkyl, benzyl, the-(CH of X to be carbonatoms be 1-10
2)
noSi (CH
3)
2(t-C
4h
9) or-(CH
2)
noH, wherein: n=1-10, t-C
4h
9for the tertiary butyl;
A is H, OR
1or SR
1in one, wherein: R
1for carbonatoms is the alkyl of 1-10;
B
1for CH
3or CF
3; B
2for CH
3, phenyl or 2-(5-phenyl) thienyl.
3. synthetic method according to claim 2, is characterized in that: step 1) described in the time of reacting under 40-100 DEG C of nitrogen atmosphere be 1-10 hour.
4. synthetic method according to claim 2, is characterized in that: step 2) described in water and the volume ratio of ethanol be 1:4.
5. synthetic method according to claim 2, is characterized in that: step 2) described in time of stirring at room temperature be 140-145 hour.
6. synthetic method according to claim 2, is characterized in that: step 2) described in the ethyl acetate of heat, the temperature of its ethyl acetate is 50 DEG C.
7. synthetic method according to claim 2, is characterized in that: step 3) described in diisopropylamine is dissolved in anhydrous diethyl ether, its diisopropylamine is dissolved in the anhydrous diethyl ether of its 3 times of volumes.
8. synthetic method according to claim 2, is characterized in that: step 4) described in organic solvent be selected from one in ethanol, methyl alcohol, tetrahydrofuran (THF) and trichloromethane.
9. synthetic method according to claim 2, is characterized in that: step 4) described in back flow reaction, be in catalyst-free or the back flow reaction of carrying out under having the catalyzer of catalytic amount to exist; Described catalyzer is piperidines or triethylamine.
10. the synthetic method according to claim 2 or 9, is characterized in that: step 4) described in time of back flow reaction be 1-10 hour.
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